Synthesis and structure of a mixed ligand complex of tris(1-phenyl-3-methyl-4-trifluoroacetyl-pyrazolone-5)bis(dimethyl sulfoxide) neodymium

A mixed ligand complex of l-phenyl-3-methyl-4-trifluoroacetyl pyrazolone-5 (HPMTFP) and dimethyl sulfoxide (DMSO) with neodymium having molecular formula Nd(PMTFP)₃ · 2DMSO has been synthesized. Its crystal and molecular structures have been determined by a four-circle X-ray diffractometer. The complex crystallizes in monoclinic with space group P 2₁/n. a = 21.897 (4), b = 23.339 (4), c = 8.958 (2)Å, β = 96.61 (3)°, Z = 4. The Nd atom is coordinated by eight oxygen atoms, which takes a distorted delta dodecahedron arrangement around the central Nd atom. The average bond length of Nd—O is 2.45 Å. The IR spectra have been discussed as well.     

Coordination compounds of neodymium(III) with acyldihydrazones of saturated dicarboxylic acids and 3-methyl-1-phenyl-4-formylpyrazol-5-one

Coordination compounds of neodymium(III) with acylhydrazones of saturated dicarboxylic acids and 3-methyl-1-phenyl-4-formylpyrazol-5-one are synthesized and studied. The structure of complex [Nd₂(H₂L²)₃] · Me₂SO · CH₃OH · 6H₂O is determined from the X-ray diffraction data for the isostructural lanthanum complex. The complex is binuclear and contains nine-vertex coordination polyhedra bound by three hydrocarbon spacers. Solid samples of the studied neodymium complexes exhibit luminescence in the near-infrared spectral range (λ = 874, 904, and 1059 nm) characteristic of this ion.     

Coordination compounds of dysprosium(III) with 3-methyl-1-phenyl-4-formylpyrazol-5-one diacyldihydrazones

Coordination compounds of dysprosium(III) with diacyldihydrazones of saturated dicarboxylic acids, imino-, oxo-, and thiodiacetic acids, and 3-methyl-1-phenyl-4-formylpyrazol-5-one (H₄L) are described. [Dy₂(H₂L^O)₃] · 7.5CH₃OH · 3H₂O was subjected to X-ray diffraction analysis: space group \(R\bar 3\) , a = 17.349(1) Å, c = 65.669(4) Å, Z = 6, R = 0.076, R _w = 0.243 (5301 reflections with I ≥ 2σ(I)). The complex is established to have a binuclear structure and contain dysprosium ions linked via three bridging ligands. The coordination polyhedron of the Dy atom had a three-capped trigonal prism geometry. The magnetic properties of the synthesized complexes were studied.     

Formation and structure of 1-Amino-4-methyl-4-(4-methyl-5-phenyl-1H-pyrazol-3-ylamino)-3-phenyl-4,5-dihydro-1H-pyrazol-5-one

The title compound 3 was obtained during the rearrangement of isoxazol-5-yl hydrazine 1 to 1-aminopyrazolone 2 at 115°. X-ray analysis of the corresponding benzylidene derivative allowed us to achieve the structure assignment.     

Thermal decomposition of iron(III) complex of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone

A pyrazolonate (PMBP) of iron(III) was prepared and its metal to ligand stoichiometry was shown to be 1∶3. The decomposition of the complex was studied by thermogravimetry and differential analyses under an air atmosphere. The complex undergos two endothermic reactions without loss in mass, at 160 and 218°C, followed by an exothermic reaction at 480°C involving decomposition of the ligands. Intermediates obtained by melting of the Fe-PMBP complex were characterized by X-ray diffraction analysis. The Fe-PMBP complex was confirmed by HPLC to be a mixture of two isomers.     

4-双(1-苯基-3-甲基-4-吡唑啉-5-酮)甲烷的晶体结构

杂环化合物1 苯基 3 甲基 4 吡唑啉 5 酮(ＨＰＭＰ)为β 二酮,不仅可用作金属离子的萃取剂,还可用于核磁共振的位移试剂,也可用于激光、催化、生化、医学等领域[1-4]。我们从ＰＭＰ出发,合成了它的Ｃｏ(Ⅱ),Ｎｉ(Ⅱ),Ｃｕ(Ⅱ)和Ｚｎ(Ⅱ)的络合物[5,6]。利用单晶Ｘ 射线衍射分析方法报道了标题化合物的晶体结构。1　实验部分在合成ＰＭＰ席夫碱化合物的过程中,得到标题化合物的单晶体。元素分析结果(括号内为计算值)Ｃ%:69 87(69 98),Ｈ%:5 62(5 59),Ｎ:15 61(15 55)。红外光谱(ＫＢｒ):1645和1637ｃｍ-1的强吸收峰归属为羰基的伸缩振动,…     

Solvent extraction of gold(III) with 1-phenyl-3-methyl-4-trifluoroacetylpyrazolone-5

A simple, rapid and selective separation procedure of gold based on its extraction with 1-phenyl-3-methyl-4-trifluoroacetylpyrazolone-5 has been developed. The dependence of the distribution ratio of gold on the pH of aqueous solutions, concentration of hydrochloric, nitric and perchloric acids and the organic solvents has been investigated. Decontamination factors for a number of metal ions with respect to gold are reported. Excellent separation of gold is obtained from many elements including noble metals. Citrate, cyanide, iodide, thiosulfate and thiourea completely mask gold, whereas oxalate does not interfere. Solutions of 1 M HCl, 0.2 M KCN, and the buffer of pH 0.8 readily strip gold from the organic phase. Some useful analytical applications of this procedure are discussed.     

Complexes of Zr(IV) and Nb(V) with 1-phenyl-3-methyl-4-benzoyl-pyrazole-5-one

The complexing of Zr(IV) and Nb(V) by 1-phenyl-3-methyl-4-benzoyl-pyrazole-5-one (HPMBzP) in various mineral acids has been studied by solvent extraction. The pyrazolone tautomers have been isolated and characterised, and the composition and structure of zirconium and niobium complexes have been established using various chemical and spectroscopic techniques.     

Thermal and spectroscopic studies of scandium complex of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone

The scandium complexes of Sc(PMBP)₃·H₂O (non-crystal) and Sc(PMBP)₃ (crystal) with 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) were prepared and characterized by thermal analysis, IR, NMR and MS spectroscopies. The crystal structure of the complex, obtained by X-ray analysis, indicates that PMBP is a bidentate ligand in the complex and that the Sc atom is six-coordinate and is in a meridional octahedral environment. The order of the ring current effect on the pyrazolone ring is Sc(PMBP)₃ >PMBP(enol)> PMBP(keto).

The metal to ligand stoichiometry was found to be 1:3. The crystalline complex melts at 209 °C, followed by degradation at about 310 °C, with the beginning of decomposition. The enthalpy of melting was found to be 61 kJ/mol. On the other hand, the non-crystalline complex was found to change into a crystalline complex at 176 °C with an exothermic reaction before melting at 217 °C. The IR band observed at approximately, 450 cm⁻¹ is possibly due to the stretching of the Sc–O bond.     

Preparation of 3(5)-phenyl-1-hydroxypyrazole 2-oxide and 4-methyl-3(5)-phenyl-1-hydroxypyrazole 2-oxide

Nitrosation of acrylophenone oxime or of methacrylophenone oxime with n-butyl nitrite in the presence of pyridine and copper(II) sulfate gives the copper complexes of the title compounds. The free 1-hydroxypyrazole 2 -oxides are isolated by treating the copper complexes with dilute sodium hydroxide, filtration, and acidification of the basic filtrates. The title compounds are the first examples of 1-hydroxypyrazole 2 -oxides in which the C3(5) ring position is unsubstituted.     

Design, synthesis and hypoglycemic activity of 3-methyl-1-phenyl-4-{4-[(5-methyl-2-phenyloxazol-4-yl)methoxy]benzylene(benzyl)}-2-pyrazol-5-one

Based on the SAR (structure activity relationship) of TZDs (thiazolidinediones), 3-methyl-1-phenyl-2-pyrazoline-5-one was selected as a substitute for TZD. Compounds of 3-methyl-1-phenyl-4-{4-[(5-methyl-2-phenyloxazol-4-yl)methoxy]benzylene(benzyl)}-2-pyrazol-5-one were designed and synthesized to find some more hypoglycemic active agents and further investigate the SAR of this class of compounds. Butanedione monoxime reacted with (substituted) benzaldehyde via cyclization and chlorination to give 4-(chloromethyl)-5-methyl-2-phenyloxazole derivatives, which condensed with 4-hydroxybenzaldehyde or vanillin, and was followed by the Knoevenagel reaction with 3-methyl-1-phenyl-2-pyrazol-5-one to give compounds Ia-Ih. Compounds Ia-Ih were hydrogenated with Pd-C to give IIa-IIh, and their hypoglycemic activity was evaluated with a glucose oxidase kit and insulin load test on normal mice. Sixteen new target compounds were synthesized. All the compounds were characterized by ¹H NMR, IR, MS and elemental analysis. The preliminary pharmacological tests show that the compounds have good hypoglycemic activity and can enhance the action of insulin, especially Ib, Id and If. __________ Translated from Chemical Journal of Chinese Universities, 2007, 28(4): 672–677 [译自: 高等学校化学学报]     

Coordination compounds of neodymium,samarium, and europium with acyldihydrazones of imino-, oxo-, and thiodiacetic acids and 3-methyl-1-phenyl-4-formylpyrazol-5-one

The coordination compounds of neodymium(III), samarium(III), and europium(III) with the acyldihydrazones of imino-, oxo-, and thiodiacetic acids and 3-methyl-1-phenyl-4-formylpyrazol-5-one were synthesized and studied. According to X-ray diffraction data, the complexes are binuclear and the lanthanide cations are linked by three binucleating ligands. The coordination polyhedra have a three-cap triangular prism geometry, the prism bases being formed by oxygen atoms and the vertices being occupied by the imine nitrogen atoms. Solid Nd(III) and Sm(III) complexes show intense luminescence in the spectral regions characteristic of these cations. Europium(III) complexes are liminescence-inactive due to the low efficiency of excitation energy transfer to the resonance levels of the central atom.     

Coordination compounds of some 3d metals with 3-methyl-1-phenyl-4-formylpyrazol-5-one

CuL₂ · 1.5H₂O and ML₂ · 2H₂O · 2EtOH (M = Co²⁺, Ni²⁺, Mn²⁺) coordination compounds were synthesized via the exchange reaction between the sodium salt of 3-methyl-1-phenyl-4-formylpyrazol-5-one (HL) and metal chlorides.The synthesized compounds were studied by thermogravimetry, magnetochemistry, and electron and IR spectroscopy. The complexes CuL₂ · 2Py and CoL₂ · 2Py · MeOH were obtained via recrystallization from a methanol-pyridine mixture, and their structures were studied by X-ray diffraction. Pyrazolone was found to be coordinated in the deprotonated enol form and to form six-membered chelate rings with a metal. The coordination polyhedron of a metal cation was found to be a square bipyramid (Cu²⁺) or an axially elongated octahedron (Co²⁺) with its vertices occupied by the oxygen atoms of 3-methyl-1-phenyl-4-formylpyrazol-5-one and the nitrogen atoms of pyridine.     

Electronic and vibrational studies of copper(II) complexes of 1-phenyl-3-methyl-4-acylpyrazolones-5

The interaction between Cu(II) and 1-pheny]-3-methyl-4-acylpyrazolones in aqueous medium has been investigated. The complexes were isolated and characterized using electronic and vibrational spectral measurments. Bathochromic shifts were observed for the complexes in the UV and infrared (IR) spectral regions. Analysis of the spectral properties of the complexes reveal that the stability of the

bond of the COCu bonding system decreases while that of the CuO bond in the same system increases as the carbon chain of the 4-acyl substituent increases. The complexes have μ_eff values within the range of 1.75–1.82 B.M.     

A Novel Photochemical Reaction of 4-Bromo-3-methyl-1- phenyl-4,5-dihydro-pyrazol-5-one

UV-Irradiation of 4-bromo-3-methyl-l-phenyl-4,5-dihydro-pyrazol-5-one (1) in the presence of various aromatic hydrocarbons gave different types of photoproducts depending on the nature of the hydrocarbons via an electron-transfer mechanism. In the presence of naphthalene or phenanthrene a photochemical homocoupling reaction of 1 occurred to form 2 or 2 and 3, respectively.     

铽与1-苯基-3-甲基-4-酰代吡唑啉-5-酮的三元配合物的合成、表征与荧光性能

合成了铽与1-苯基-3-甲基-4-异丁酰基吡唑啉-5-酮(HPMIBP)、1-苯基-3-甲基-4-苯甲酰基吡唑啉-5-酮(HPMBP)的四个三元配合物Tb(PMIBP)3.2H2O(A1), Tb(PMIBP)3.bpy(A2), Tb(PMBP)3.2H2O(B1)和Tb(PMBP)3.bpy(B2)(bpy=2, 2'-联吡啶)。用元素分析确定了它们的组成, 并用紫外-可见光谱、红外光谱、差热-热重谱对其进行了表征。研究了它们在固态和溶液中的荧光光谱, 并用频域法测定了它们在溶液中的荧光寿命, 结果表明A1和A2的荧光强度比相应的B1和B2强三个数量级, A2与A1或B2与B1相比, 荧光强度也有一定程度的增强,并且不同溶剂对其荧光强度和荧光寿命都有较大的影响。