Copper(II) complexes with ligands derived from 4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one: synthesis and biological activity

The synthesis of Cu(II) complexes derived from Schiff base ligands obtained by the condensation of 2-hydroxybenzaldehyde or terephtalic aldehyde with 4-amino-antipyrine (4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one) is presented. The newly prepared compounds were characterized by( 1)H-NMR, UV-VIS, IR and ESR spectroscopy. The determination of the antimicrobial activity of the ligands and of the complexes was carried out on samples of Escherichia coli, Klebsiella pneumoniae, Acinetobacter boumanii, Pseudomonas aeruginosa, Staphylococcus aureus and Candida sp. The qualitative and quantitative antimicrobial activity test results proved that all the prepared complexes are very active, especially against samples of Ps. aeruginosa, A. Boumanii, E. coli and S. aureus.     

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) , V = 1937.1(7) 3, Z = 4, Dc = 1.260 g/cm3, 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 Trans-4-[(5-(2,4-Dichlorophenoxy)-3-methyl-1-phenyl-1H-pyrazol-4-yl)methyleneamino]-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one

The title compound trans-4-[(5-(2,4-dichlorophenoxy)-3-methyl-1-phenyl-1H-pyra-zol-4-yl)methyleneamino]-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 3 (C28H23Cl2N5O2, Mr = 532.41) has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1 with a = 8.9438(4), b = 11.6065(5), c = 14.2215(6) , α = 112.566(1), β = 92.324(2), γ = 102.91(1)o, V = 1315.65(10) 3, Z = 2, Dc = 1.344 g/cm3, μ(MoKα) = 0.282 mm-1, λ = 0.71073 , F(000) = 552, the final R = 0.0587 and wR = 0.1578 for 5071 observed reflections (I > 2σ(I)). X-ray analysis reveals that the product is a thermodynamically stable trans isomer. Intra-and intermolecular C(12)-H(12)···O(1) and C(28)-H(28)···O(1)#1 hydrogen bonds were observed in the title compound.     

1－苯基－3－甲基－4－（6－氢－4－氨基－5－硫杂－2，3－吡嗪）－吡唑啉酮光致变色超分子化合物的合成、结构与性能

通过1－苯基－3－甲基－4－氯乙酰基－吡唑啉酮－5（PMCP）和氨基硫脲（ TSC）缩合，形成了一种含NNS六元杂环的光致变色化合物（PMCP－TSC）。利用元 素分析，MS，”1H NMR，IR和UV光谱进行了表征。通过紫外可见光谱对它的光致 变色性质进行了研究，测出了光致变色反应的动力学常数。并用X线单晶衍射仪测 定了PMCP－TSC变色后的晶体结构，该晶体属单斜晶系，具有P2_1/c空间群，a = 0.105 10(2) nm, b = 0.150 61(3) nm, c = 0.993 70(10) nm, β = 107.890 (10)°, V = 1.496 9(4) nm~3, Z - 4, D_c = 1.417 Mg/m~3, μ = 0.232 mm~(- 1), F(000) = 672, R = 0.033 4, wR = 0.089 6。结构分析表明：其光致变色现 象是由于它在溶剂与光的共同作用下发生了从醇式到酮式的异构化。同时该化合物 经分子间氢键形成二聚体，又通过甲醇与本体分子之间的氢键使化合物形成具有三 维网络结构的超分子化合物。     

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/cm3,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) pheny1 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.     

O-Alkylation of 3-hydroxy-1-phenyl-2-pyrazolin-5-one

3-Hydroxy-1-phenyl-2-pyrazolin-5-one 1 reacts with primary, secondary and allylic alcohols under catalytic acidic conditions and in the presence of 3 Å molecular sieves, to afford 3-alkoxy-1-phenyl-2-pyrazolin-5-ones 3 .     

Alkyldithiocarboxylation of 3-hydroxy-1-phenyl-2-pyrazolin-5-one

4-Alkyldithiocarboxylate-3,5-dihydroxy-1-phenylpyrazoles 2, are prepared in good yield by the reaction of 3-hydroxy-1-phenyl-2-pyrazolin-5-one 1 with sodium acetate in dimethylformamide (DMF), carbon disulfide and alkyl halides.     

Structure of 1-phenyl-1-thioxo-2,5-dimethyl-3-morpholinomethyl-phosphorinan-4-one

Chemical Sciences Institute, Kazakh Academy of Sciences. Institute for Heteroorganic Compounds, USSR Academy of Sciences. Translated from Zhurnal Strukturnoi Khimii, Vol. 31, No. 1, pp. 184–186, January–February, 1990.     

3-甲基-5-氰基-6-氨基-1-苯基-4-(3,4-二甲氧基苯基)-1,4-二氢吡喃[2,3-c]吡唑的合成和晶体结构

标题化合物C22H20N4O3 3是由2-氰基-3-(3,4-二甲氧基苯基)丙烯腈1和3-甲基-1-苯基-2-吡唑-5-酮2在KF-Al2O3催化下在N,N-二甲基甲酰胺(DMF)溶剂中反应而得。结构通过单晶X-射线衍射分析确定,其晶体属于三斜晶系,空间群Pī,a = 9.450(3),b = 10.876(2), c = 11.435(2) ,a = 115.51(1), b = 102.82(1),g = 98.47(2), Mr = 388.42, V = 994.1(3) 3,Dc = 1.298 g/cm3, Z = 2, m (MoKa) = 0.089 mm-1, F(000) = 408。晶体结构用直接法解出,使用全矩阵最小二乘法对原子参数进行修正,最后的偏离因子R = 0.0420,wR = 0.1070。单晶X-射线衍射分析表明平面Ⅰ与平面Ⅱ、平面Ⅲ、平面Ⅳ的夹角分别为102.31、29.24和1.43。平面Ⅱ与平面Ⅲ和平面Ⅳ的夹角分别为73.50和100.91,平面Ⅲ和平面Ⅳ的夹角为27.81, 另外晶体中还存在分子间氢键。     

Spirobutyrolactone derived from 1-phenyl-3-methyl-2-pyrazolin-5-one

X-ray diffraction and NMR spectral examination have shown that 1-phenyl-3-methyl-2-pyrazolin-5-one reacts with methyl acrylate in methanol to give spiro[(1-phenyl-3-methyl-2-pyrazolin-5-one)-4,5-butyrolactone]. The conformation has been shown to be the same in the crystal and in solution, the pyrazoline ring has been found to be nonplanar, the reasons for the acoplanarity established, stabilizing and destabilizing interactions studied, and the orientation of the phenyl substituent relative to the pyrazolin-5-one ring determined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 909–913, July, 1988.     

Synthesis and Crystal Structure of 3-Benzoyl-7,7-dimethyl-4-phenyl-2-phenylamino-4,6,7,8-tetrahydro-chromen-5-one

The title compound (C30H27NO3) was synthesized via a one-pot procedure starting from β-benzoylthioacetanilide, benzaldehyde and 5,5-dimethyl-1,3-cyclohexanedione, and its struc- ture was determined by single-crystal X-ray diffraction analysis. The crystal belongs to triclinic system, space group P, with a = 6.325(2), b = 11.243(3), c = 17.553(4) , α = 87.306(4), β = 80.822(4), γ = 77.798(4)°, V = 1204.2(5) 3, Z = 2, Mr = 449.53, Dc = 1.240 g/cm3, μ = 0.080 mm-1, F(000) = 476, the final R = 0.0459 and wR = 0.0970 for 2301 observed reflections with I > 2σ(I).     

1-苯基-3-甲基-4-(6-氢-4-甲基氨基-5-硫杂-2,3-吡嗪)-吡唑啉酮的合成与晶体结构

通过1-苯基-3-甲基-4-氯乙酰基-吡唑啉酮-5 (PMCP) 和4-甲基氨基硫脲 (MTSC) 缩合, 形成了一种新的双杂环化合物 (PMCP-MTSC)。利用元素分析与单晶X-射线衍射进行了表征。 该化合物(C14H15N5OS)属单斜晶系, P21 空间群, 晶体学参数为 a = 7.634(1), b = 11.639(2), c = 8.150(2) ? ?= 98.13(1), V = 716.9(2) ?, Z = 2, Dc = 1.396 g/cm3, (MoKa) = 0.232 mm-1, F(000) = 316, Mr = 301.37。结构由直接法解出,共收集3114个衍射点,其中I > 2(I)的独立衍射点有2453个,用全矩阵最小二乘法修正,最终偏离因子:R = 0.0294, wR = 0.0738。结构分析表明: 该化合物以酮式存在,分子间通过氢键作用(N(5)H…O)连接起来并形成一维链状结构。     

Palladium(II) complexes of Schiff bases derived from 5-amino-2,4-(1H, 3H)pyrimidinedione (5-aminouracil) and 1,2-dihydro-1,5-dimethyl-2-phenyl-4-amino-3H-pyrazol-3-one

Summary New palladium(II) complexes of Schiff bases, obtained from 5-aminouracil, (AUH), and acetylacetone (AUAcAcH₂), benzaldehyde (AUBALH), furan-2-aldehyde (AUFALH), 2-hydroxynaphthaldehyde (AUNALH₂), pyridine-2-aldehyde (AUPyALH) or salicylaldehyde (AUSALH₂) and from 1,2-dihydro-1,5-dimethyl-2-phenyl-4-amino-3H-pyrazol-3-one (AAPy) and acetylacetone (AAPyAcAcH), 2-hydroxyacetophenone (AAPyAPH), furan-2-aldehyde (AAPyFAL), pytidine-2-aldehyde (AAPyPyAL), or salicylaldehyde (AAPySALH), have been prepared. The complexes, with formulae PdL₂Cl₂ (L=AUBALH, AUFALH or AUSALH₂); PdLCl₂ (L=AUAcAcH₂, AUNALH₂, AUPyALH, AAPyFAL or AAPyPyAL) and PdLCl (L=AAPyAcAc or AAPySAL) were characterized by elemental analysis, i.r. and electronic spectral studies, thermogravimetric analyses and magnetic and conductance measurements. The x-ray powder diffraction pattern of one of the complexes was also examined. The complexes were screened for their possible antitumour activityin vitro.