Synthesis, Characterization and Activity of Rare Earth Complexes with Schiff Base From 2,6-Diformylpyridine N-Oxide and 4-Amino-antipyrine

Six new rare earth complexes with Schiff base from 2,6 diformylpyridine N oxide and 4 amino antipyrine were synthesized. These complexes with general formula REL(NO 3) 3 (RE=La, Pr, Eu, Tb, Er, Y) were characterized by elemental analysis, IR, UV, molar conductance measurements and antimicrobial activity.

Synthesis of Novel 4-Thiazolidinone and Bis-Thiazalidin-4-One Derivatives Derived from 4-Amino-Antipyrine and Evaluated as Inhibition of Purine Metabolism Enzymes by Bacteria

Novel 4-thiazolidione and 1,4-bis-thiazolidinone derivatives bearing antipyrine moiety have been obtained from condensation of 4-aminoantipyrine 1 with aromatic/heteroaldehydes followed by cycloaddition with mercaptoacetic acid in nonpolar solvents. Structure of the products has been deduced upon their elemental analysis and spectral measurements. Most of the targets evaluated as enzymatic effect towards some bacteria (E. coli) in compare with Xanthine oxidase (from buttermilk) where the role of compounds is an inhibition of purine metabolism enzymes caused by E. coli.

STUDIES On THE SOLID-STATE PHOTOCHEMICAL RFACTIONS OF ANTIPYRINE WITH AROMATIC ALDEHYDE

Solid state photochemical reactions of antipyrine with 5-formyl-1,3- dimethyluracil,p-nitrobenzaldehyde and p-hydroxybenzaldehyde have been described.The structures of 4 hey compounds obtained were determined by IR,UV,\+1HNHR,ns and elemental analysis.

晶体Zn(antipyrine)_2(NO_3)_2∶VO^(2+)的EPR谱及光吸收谱的理论研究

由于硝酸钒锌二安替比林晶体[Zn(antipyrine)2(NO3)2∶VO2+]中配体O2-的自旋-轨道耦合参量0pζ≈150cm-1与中心过渡族3d1离子V4+的ζ0d≈248 cm-1相差不太大,故配体的自旋-轨道耦合参量0pζ对电子顺磁共振(EPR)谱和光吸收谱的贡献必须考虑。采用双自旋-轨道耦合参量模型和相关的晶体场能级公式,计算了Zn(antipyrine)2(NO3)2∶VO2+晶体的EPR谱和光吸收谱,所得理论结果与实验发现很好符合;确定了该晶体的局域对称结构沿C4轴的四角畸变约为0.45 nm;计算发现,较大的κ值说明VO2+中未配对的s电子对超精细结构常数有较大的贡献。并对上述这些结果的合理性进行了讨论。

Influencing factors and degradation products of antipyrine chlorination in water with free chlorine

Owing to its low cost, free chlorine is one of the most common disinfectants for wastewater and drinking water treatment. However, the formation of disinfection byproducts has been found to occur after free chlorine disinfection in recent decades. Antipyrine （ANT）, an anti-inflammatory analgesic, has been frequently detected in the aquatic environment. In this work, the removal efficiency of ANT by free chlorine oxidation in ultrapure water was investigated with batch experiments. The influencing factors on the removal of ANT were explored at initial concentrations of ANT from 0.04 to 0.64 rag/L, free chlorine dosage from 0.30 to 1.31 rag/L, and pH from 1.5 to 9.0. The main degradation products were identified by solid phase extraction-gas chromatography-mass spectrometry. The results showed that ANT reacted rapidly with free chlorine in ultrapure water systems and up to 90.6% removal efficiency of ANT was achieved after 25 sec （initial free chlorine 1 mg/L, ANT 0.5 mg/L, pH 7.0）. Higher oxidant dosage, lower ANT initial concentration and low pH favor the ANT removal. The main degradation product in ANT chlorination was a monochlorine substitution product （4-chloro-l,2-dihydro- 1,5-dimethyl-2-phenyl-3H-pyrazol-3-one）, which can be further chlorinated by free chlorine. In addition, the total organic carbon result indicated that ANT is difficult to be mineralized using chlorine.

Degradation of antipyrine in the Fenton-like process with a La-doped heterogeneous catalyst

The aim of this study was to synthesize a novel lanthanum(La)doped catalyst and to investigate antipyrine removal in wastewater using the Fenton-like process with the catalyst.The La-doped Co-Cu-Fe catalyst was synthesized using the modified hydrothermal method.Results showed that the Ladoped catalyst had higher specific surface area and lower particle size than the catalyst without La doping(i.e.,the control)(267 vs.163 m2/g and 14 vs.32 nm,respectively).Under the conditions of catalyst dosage 0.5 g/L,H2O2 concentration 1.70 g/L,and NaHCO3 0.1g/L,the antipyrine removal within 60 min using the Fenton-like process with the La-doped catalyst was much higher than that with the control(95%vs.54%).The hydroxyl radical concentration with the La-doped catalyst within 60 min was two times higher than that with the control(49.2 vs.22.1 gg/L).The high catalytic activity of La-doped catalyst was mainly attributed to its high specific surface area based on the X-ray photoelectron spectroscopy result.Our La-doped catalyst should have great potential to remove antipyrine in wastewater using the heterogeneous Fenton-like process.

Synthesis of Antipyrine Derivatives Derived from Dimedone

Coupling of dimedone with the diazonium salt of 4-aminoantipyrine afforded 2,3-dimethyl-4-[2-（5,5-dimethyl- 2,6-dioxocyclohex-2-ylidend）-hydrazino]-5-oxo-1-phenylpyrazoline （3）. Reaction of 3 with excess phenylhydrazine gave the mixed trishydrazone derivative 4. Treatment of 3 with hydroxylamine produced the bisoxime 5 which upon dehydrative cyclization with acetic anhydride gave the corrsponding tetrahydrobenzo[d][1,2,3]triazole derivative 7. A one-pot synthesis of 7 was done by reacting 3 with hydroxylamine hydrochloride in pyridine, followed by heatment with acetic anhydride.

Study on the synthesis and crystal structure of tetrahyhrated tetraaquotris(4-mono-chloroacetylantipyrine)samarium (Ⅲ) perchlorate

Based on the phase equilibrium study of the system Sm(ClO4)3-4-monochloroace-tylantipyrine (C13H13ClN2O2)-H2O at 30℃, we have synthesized the title complex [Sm(C13H13Cl. N2O2)3(H2O)4](C1O4)3.4H2O. The single crystal structure analysis on RASA-IIS Rigaku diffrac-tometer shows that the coordination number of the metal ion is nine and the geometry of the complex is tricapped trigonal prism. Two of the three molecules of organic ligand act as bidentate chelated through both carbonyl oxygens to the metal ion, but the other one as a monodentate coordinated only through the ring carbonyl oxygen, the side chain carbonyl is far away from the central ion. The crystal is monoclinic, space group P21, a = 18.013(4), 6 = 14.709(3), c = 10.536(3) A, β=94.69(2)°, V=2782(1) A3, Z=2.

1,5-Dimethy-4-[(3-nitro-benzylidene)-amino]-2-pheyl-1,2-dihydro-pyrazol-3-one

The title compound C18H16N4O3 （Mr = 336.35） has been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The Schiff base compound is a derivative of 4-aminoantipyrine. As expected, the molecular structure adopts a trans configuration about the central C=N double bond. It crystallizes in orthorhombic, space group P2dc with a = 7.632（1）, b = 7.816（1）, c = 28.082（5） A,β = 96.18（1）°, V= 1665.48（51） A^3, Z= 4, Dc = 1.341 g/cm^3, F（000） = 704,μ = 0.094 mm^-1, the final R = 0.0448 and wR = 0.1058. Of the total 3748 collections, 3105 were unique. In the molecule there exist two different planes of pyrazoline and C（11）-C（16） phenyl ring, which are approximately coplanar （r.m.s. de deviation from the combined mean plane is 0.03 A） with the dihedral angle between them of 9.8%.

Synthesis and Crystal Structure of 4-[(1E)-(4-Hydroxy-3,5-dimethoxybenzylidene)-amino]-1,5-dimethyl-2-phenyl-2,3-dihydro-1H-pyrazol-3-one

The title compound （C20H21N3O4, Mr = 367.40） has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction. The crystal is of orthorhombic, space group P212121 with a = 7.5143（15）, b = 13.901（3）, c = 18.545（4）A , V = 1937.1（7） A^3, Z = 4, Dc = 1.260 g/cm^3, μ = 0.089 mm^-1, F（000） = 776, the final R = 0.0616 and wR = 0.0912. X-ray diffraction reveals that the molecule adopts an E configuration about the central C=N double bond. The intermolecular O-H…O hydrogen bond stabilizes the crystal structure by causing the formation of a supramolecular architecture.

Synthesis and Crystal Structure of 4-{[(1E)1-(2-Hydroxy-3-methoxyphenyl)methylidene]amino}-1,5-dimethyl-2-phenyl-2,3-dihydro-1H-pyrazol-3-one

The title Schiff base compound, C19H19N3O3, a derivative of antipyrine, has been synthesized and characterized by elemental analysis, IR, and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group C2/c, with α = 27.935（5）, b = 7.553（1）, c = 16.692（3） A, β = 105.810（3）°, Z = 8, V= 3388.7（10） A^3, Dc = 1.323 g/cm^3, Mr = 337.37, λ（MoKα） = 0.71073 A,μ= 0.091 mm^-1, F（000） = 1424, R = 0.0630 and wR = 0.1273. A total of 3513 unique reflections were collected, of which 2112 with I 〉 2σ（I） were observed. The molecular structure adopts a trans configuration about the C=N double bond. The pyrazoline and C（1）-C（6） phenyl ring are approximately coplanar （mean deviation from the combined plane is 0.069（3） A）, with the dihedral angle of 9.7（2）°. The preliminary biological tests show that the compound has high antibacterial activities.

4-[(Furan-2-ylmethylene)-amino]-1,5-dimethyl-1,2-dihyl-1,2-dihydo-pyrazol-3-one

The title compound （C16H15N3O2, Mr= 281.31） has been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The Schiff base compound is a derivative of 4-aminoantipyrine. As expected, the molecular structure adopts a trans configuration about the C=N double bond. It crystallizes in the monoclinic system, space group P2 1/c with a = 11.150（3）, b = 9.906（3）, c = 13.624（4） A, β = 106.360（4）°, V= 1443.9（7） ,A^3, Z = 4, Dc = 1.294 g/cm^3, F（000） = 592,μ（MoKa） = 0.088 mm ^-1, R = 0.0577 and wR = 0.1214. Of the 5766 total reflections, 2540 were unique. In the molecule there exist two different planes of pyrazoline and O（2）-C（10） phenyl ring, which are approximately coplanar （r.m.s. de deviation from the combined mean plane is 0026 A） with the dihedral angle between them of 6.3°.