Synthesis and Crystal Structure of a Copper(II) Compound Constructed by N-(4,6- Dimethoxylpyrimidin)-N'-(ethoxycarbonyl)thiourea

A copper(Ⅱ) complex Cu(L)2(NO3)2 constructed by the L (L = N-(4,6-dime- thoxylpyrimidin)-N'-(ethoxycarbonyl)thiourea) ligand crystallizes in monoclinic, space group C2/c with a = 16.2416(16), b = 9.1385(7), c = 22.0008(18) (A),β = 108.077(2)°, V ＝ 3104.3(5)(A)3, Dc = 1.627 g/cm3, Z = 4, C20H28CuN10O14S2, Mr = 760.18, μ(MoKα) = 0.920 mm-1, F(000) = 1564, R = 0.0471 and wR = 0.1284 for 2239 observed reflections (I > 2σ(I)). X-ray diffraction shows the existence of weak complementary intramolecular N-H…O (DA) hydrogen bonds which further strengthen the coordination from the two L ligands with the Cu(II) ion, intermolecular C-H…O hydrogen bonds and weak π…π stacking interactions, leading to the formation of a multi-dimen- sional supramolecular network.     

N─苯基邻苯二甲酰亚胺和N─对甲苯基邻苯二甲酰亚胺的晶体和分子结构

报道一种新类型的有机电子晶体Ｎ－苯基邻苯二甲酰亚胺（１）（Ｃ＿（１４）Ｈ＿９ＮＯ＿２）和Ｎ－对甲苯基邻苯二甲酰亚胺（２）（Ｃ＿（１５）Ｈ＿（１１）ＮＯ＿２）的晶体和分子结构，（１）属正交晶系，空间群为Ｐｃａｂ，ａ＝７．６４９（４），ｂ＝１１．６５９（２），ｃ＝２３．７３９（３）Ａ，Ｖ＝２１１７．０Ａ￣３，Ｚ＝８，Ｄ＿ｃ＝１．４０１ｇ／ｃｍ￣３，Ｍ＿ｒ＝２２３．２３，μ＝０．８８５ｃｍ￣（－１），最终偏离因子Ｒ＝０．０５３，Ｒ＿ω＝０．０４８；（２）属正交晶系，空间群为Ｐｎａ２＿１，ａ＝７．６２４（２），ｂ＝１１．２３７（１），ｃ＝１３．８５６（２）Ａ，Ｖ＝１１８７．０　Ａ３，Ｚ＝４，Ｄ＿ｃ＝１．３２８ｇ／ｃｍ￣３，Ｍｒ＝２３７．２６，μ＝２．７６４ｃｍ－１，最终偏离因子Ｒ＝０．０３６，Ｒ＿ω＝０．０３２。晶体结构测定结果表明，邻苯二甲酰亚胺的内酰亚胺碳、氮、氧原子与其苯并环共平面。化合物（２）中的甲基碳原子与取代基苯环共平面，苯并酰亚胺平面与取代苯环平面间的夹角分别为５８．４°（化合物１）和５６．２°（化合物２）。     

新型N-取代苯甲酰基-N′-(4-甲基苯并噻唑-2-基)硫脲衍生物的合成、晶体结构及抑菌活性

以取代苯甲酸和2-氨基-4-甲基苯并噻唑为原料合成5个新型N-取代苯甲酰基-N′-(4-甲基苯并噻唑-2-基)硫脲衍生物,化合物结构经元素分析、IR、1 H NMR和13 C NMR表征,X-射线单晶衍射测定了N-(4-甲氧苯甲酰基)-N′-(4-甲基苯并噻唑-2-基)硫脲(化合物1)的晶体结构,该晶体为单斜晶系,P21/c空间群,选择广西主要经济作物中常见的病原菌,对目标化合物进行室内抑菌活性测试,实验结果发现该类化合物具有一定的抑菌活性.     

N-(P-羟甲基苯基)咔唑丙烯酸酯的合成和聚合

<正> 为了深入认识含咔唑基单体的光敏性与聚合性的关系,在本系列含咔唑基化合物的基础上,合成了两个新单体:N-(p-羟甲基苯基)咔唑丙烯酸酯和N-(P-羟甲基苯基)咔唑甲基丙烯酸酯,并研究了其聚合行为。 化合物Ⅰ、Ⅱ、Ⅲ和聚合物的合成,反应式如下:     

Asymmetric Morita-Baylis-Hillman reactions of 2-cyclohexen-1-one catalyzed by chiral biaryl-based bis(thiourea) organocatalysts

Newly-developed bis(thiourea) 1d was found to be an efficient organocatalyst for the Morita-Baylis-Hillman reaction. High enantioselectivities were obtained in the reaction of 2-cyclohexen-1-one with both aromatic aldehydes (up to 84% ee) and aliphatic aldehydes (up to 96% ee).     

Thermochemical and thermal analysis on N-(p-methylphenyl)-N'-(2-pyridyl)urea

Low temperature heat capacities of N-(p-methylphenyl)-N'-(2-pyridyl)urea were determined by adiabatic calorimetry method in the temperature range from 80 to 370 K. It was found that there was not any heat anomaly in this temperature region. Based on the experimental data, some thermodynamic function results were obtained. Thermal stability and decomposition characteristics analysis of N-(p-methylphenyl)-N'-(2-pyridyl)urea were carried out by DSC and TG. The results indicated that N-(p-methylphenyl)-N'-(2-pyridyl)urea started to melt at ca. 426 K (153°C) and the melting peak located at 447.01 K (173.86°C). The melting enthalpy was 204.445 kJ mol^-1 (899.6 J g^-1). The decomposition peak of N-(p-methylphenyl)-N'-(2-pyridyl)urea was found at 499.26 K (226.11°C) from DSC curve. This result was similar with that from TG and DTG experiment, in which the mass loss peak was determined as 500.4 K (227.2°C). This revised version was published online in August 2006 with corrections to the Cover Date.     

Complexes of cobalt(2+) chloride with hydrochlorides of N-(1,2,4-triazol-5-yl)- and N-(tetrazol-5-yl)benzamidines

We have synthesized complex compounds of Co(2+) chloride with hydrochlorides of N-(1,2,4-triazol-5-yl)benzamidine and N-(tetrazol-5-yl)benzamidine. According to magnetochemistry and electron spectroscopy data, the ligands are coordinated in a bidentate fashion with the N atom of the amidine group and the N atom of the heterocycle with formation of the tetrahedral chromophore CoN₂Cl₂.Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, 630090 Novosibirsk. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2311–2315, October, 1992.     

Crystal Structure and Biological Activities of N-（5-（4-Chloro-2-（trifluoromethyl）phenyl）furan-2-carbonyl）-N＇-（4,6,dimethylpyrimidin-2-yl）thiourea

The new title compound N-（5-（4-chloro-2-（trifluoromethyl）phenyl）furan-2-carbon-yl）- N＇-（4,6-dimethylpyrimidin-2-yl）thiourea （C19H14C1F3N4O2S） has been synthesized, and its crystal structure and biological behaviors were studied. The title compound crystallizes in the monoclinic system, space group P21/c with a = 7.932（5）, b = 33.46（2）, c = 7.556（5） A, β = 98.058（9）°, V = 1986（2） A^3 Mr = 454.85, Z = 4, Dc = 1.521 g/cm^3, μ = 0.349 mm^-1 and F（000） = 928. The structure was solved by direct methods and refined to R = 0.0724 and wR= 0.1429 for 3494 observed reflections （I 〉 2σ（I））. Intermolecular hydrogen bonds along the b axis together with the continuous π-π interactions construct the three-dimensional architecture of the title compound. The preliminary biological tests show definite herbicidalactivity for the title compound.     

Polystyrene bis[N-(2-pyridyl) sulfonamide] palladium(II): Synthesis,characterization as a catalyst for coupling reactions

The [N-(2-pyridyl)] para-styrene sulfonamide (PSS) was prepared as a monomer, from the reaction of para-styrene sulfonyl chloride and 2-amino pyridine in the presence of potassium hydroxide solution 0.5 M as a base, and CH₃Cl. Polystyrene [N-(2-pyridyl) sulfonamide] (PPSS) was synthesized from the polymerization of [N-(2-pyridyl)] para-styrene sulfonamide (PSS). The Polystyrene bis [N-(2-pyridyl) sulfonamide] palladium (II) as a polymer- supporting palladium complex was also prepared from the reaction of PdCl₂ (CH₃CN)₂ with PPSS in the presence of KOH 0.5 M. Polystyrene bis [N-(2-pyridyl) sulfonamide] palladium (II) is produced as a novel heterogeneous catalyst for coupling reactions for C-C bond formation. This method includes higher yield and has an easier work-up procedure. The structures of the monomer, polymer and its Pd complex were confirmed by using FT-IR and ¹H-NMR spectroscopy. Elemental analysis of Pd by inductively coupled plasma (ICP) technique and hot filtration test showed loading of the metal into solution from the catalyst The heterogeneous catalyst was recycled without any loss in its properties.     

Crystal Structure and Biological Activities of N-(5-(4-Chloro-2-(trifluoromethyl)phenyl)furan-2- carbonyl)-N'-(4,6-dimethylpyrimidin-2-yl)thiourea

The new title compound N-(5-(4-chloro-2-(trifluoromethyl)phenyl)furan-2-carbon-yl)- N?-(4,6-dimethylpyrimidin-2-yl)thiourea (C19H14ClF3N4O2S) has been synthesized, and its crystal structure and biological behaviors were studied. The title compound crystallizes in the monoclinic system, space group P21/c with a = 7.932(5), b = 33.46(2), c = 7.556(5) , β = 98.058(9)°, V = 1986(2) 3, Mr = 454.85, Z = 4, Dc = 1.521 g/cm3, μ = 0.349 mm–1 and F(000) = 928. The structure was solved by direct methods and refined to R = 0.0724 and wR = 0.1429 for 3494 observed reflections (I > 2σ(I)). Intermolecular hydrogen bonds along the b axis together with the continuous π-π interactions construct the three-dimensional architecture of the title compound. The preliminary biological tests show definite herbicidal activity for the title compound.     

Complexation of copper(I) by thiourea in acidic aqueous solution

The interaction of copper(II) and copper(I) with thiourea(Tu) has been investigated by UV and visible spectrophotometry. Over the range of concentrations of copper(I) and Tu(0.1–20)×10^–3 mol-dm^–3 in acid aqueous solutions there are two complexes, CuTu₂ ⁺ (log ₂=11.1) and the other has the ratio Cu/Tu=1/1 with the likely composition Cu₂Tu₂ ²⁺ with log ₂₂=18.5. By the determination of copper(0) solubility in acid thiourea solution and potentiometric measurements it was shown that the potential of the copper electrode is that of a non-equilibrium (corrosive) electrode.     

Acid-catalyzed Conversions of N-(4-Nitrobenzylidene)-2-cyclopropyl- and N-(4-Nitrobenzylidene)-2-alkenylanilines. A new Method for the Synthesis of Dihydroquinolines and Quinolines

The acid-catalyzed conversions of N-(4-nitrobenzylidene)-2-cyclopropyl- and N-(4-nitrobenzylidene)-2-alkenylanilines have been studied. It has been established that the protonated azomethine unit of N-(4-nitrobenzylidene)-2-cyclopropylanilines is not capable of initiating intramolecular heterocyclization with participation of the three-membered ring. Conversion of N-(4-nitrobenzylidene)-2-(1-methylcyclopropyl)aniline to derivatives of quinoline is possible under the influence of concentrated H₂SO₄. Under the same conditions 2-methylcyclopropyl- and cyclopropyl-substituted Schiff's bases form only the corresponding alkenylazomethines (isomerization of the three-membered ring). Under the influence of more moderate acids (trifluoroacetic, polyphosphoric) N-(4-nitrobenzylidene)-2-propenyl- and N-(4-nitrobenzylidene)-2-buten-2-yl)anilines are converted to the corresponding dihydroquinolines and quinolines in high yields. N-(4-Nitrobenzylide! ne)- 2-(2,2-dimethylvinyl)aniline does not form derivatives of quinoline under the influence of the same acids in the given conditions.     

Asymmetric Synthesis of N-（Diphenylphosphinyl）furfurylamine by the Enantioselective Alkylation of Furfurylimine

Optically active N-（diphenylphosphinyl）furfurylamines 2 with good ee values were obtained by the enantioselective addition of dialkylzincs to furfuryl imine 1 in the presence of chiral aminoalcohol derivatives and oxazolines.     

Studies on the Synthesis,Crystal Structure and Antitumor Activities of Mn(II) Complex Derived from the Desulfurization of N-(p-nitrophenyl)-N′-(methoxycarbonyl)thiourea and o-Phenanthroline

One new Mn(II) complex, 1, MnL₂(phen)₂ (L = p-nitrophenylcyanamido-N, phen = o-phenanthroline) has been synthesized and crystallographically characterized. Complex 1 was obtained from the desulfurization and hydrolysis of H₂pmt (H₂pmt = N-(p-nitrophenyl)-N′-(methoxycarbonyl)thiourea) in alkaline media. 1 crystallized in the triclinic space group P-1 with a = 11.0320(3), b = 11.7831(4), c = 12.9288(4) Å; α = 87.3590(10), β = 81.7500(10), γ= 84.0080(10)°. Preliminary pharmacological tests showed that complex 1 exhibited definite inhibition activities against human ovary tumor 3A0 and mice P388 in vitro.     

Fluorescent investigation of the interactions between N-(p-chlorophenyl)-N'-(1-naphthyl) thiourea and serum albumin: synchronous fluorescence determination of serum albumin

The interactions between N-(p-chlorophenyl)-N′-(1-naphthyl) thiourea and serum albumin were investigated by fluorescence spectroscopy and UV absorption spectrum under physiological conditions. The results of spectroscopic measurements suggested that N-(p-chlorophenyl)-N′-(1-naphthyl) thiourea should have a strong ability to quench the intrinsic fluorescence of both bovine serum albumin and human serum albumin through static quenching procedure, and the hydrophobic interaction was the predominant intermolecular force stabilizing the complex. Thermodynamic parameter enthalpy changes (ΔH) and entropy changes (ΔS) were calculated according to the Vant’Hoff equation. The binding distances between N-(p-chlorophenyl)-N′-(1-naphthyl) thiourea and the proteins were evaluated on the basis of the theory of Föster energy transfer. In addition, the effects of other ions on the binding constants of complexes were also discussed. Synchronous fluorescence technology was successfully applied to the determination of serum albumins added to the CPNT solution.     

Sulfanyl chloride induced heterocyclization of N-(pyrazolyl)styrylacetamides

Heterocyclization of N-(pyrazol-3-yl)styrylacetamides with arenesulfenyl chlorides yields the corresponding tetrahydrofuran-2-iminium perchlorates isolable after chromatography as trans-5-aryl-4-(arylthio)tetrahydrofuran-2-ones and 5-aryl-4-(arylthio)-1-(pyrazol-3-yl)pyrrolidin-2-ones, with the latter predominating. N-(Pyrazol-4-yl)styrylacetamides react under analogous conditions to give 5-aryl-4-(arylthio)-1-(pyrazol-4-yl)pyrrolidin-2-ones, 4-aryl-3-(arylthio)-4-chloro-N-(1-methylpyrazol-4-yl)butanamides, and tetrahydrofuran-2-iminium perchlorates which, when chromatographed, produce 5-aryl-4-(arylthio)dihydrofuran-2(3H)-ones and 4-aryl-3-(arylthio)-4-methoxy-N-(1-methyl-1H-pyrazol-4-yl)butanamides.     

Thermal stability and degradation of poly(N-(4-chlorophenyl) acrylamide) homopolymer and copolymer of N-(4-chlorophenyl) acrylamide with methyl methacrylate

Different concentrations of copolymer of (N-(4-chlorophenyl) acrylamide) (CA) with methyl methacrylate (MMA) were prepared and the reactivity ratio values of copolymerization were calculated using ¹H NMR technique. Thermal analysis of the copolymers showed that the thermal stability is intermediate between poly(N-(4-chlorophenyl) acrylamide) (PCA) and poly(methyl methacrylate) (PMMA) homopolymers. Thermal degradation products of the PCA were identified by GC–MS techniques. It seems that the mechanism of degradation of PCA homopolymer is characterized by free radical formation followed by recombination along the backbone chain. The activation energies of the thermal degradation of the copolymers were calculated using Arrhenius relationship.     

Thermal-Induced Dimerization Cyclization of Ethyl N-(Styrylcarbamoyl)acetates: Formation of 4-Hydroxy-2(1H)-pyridone-3- carboxamide Derivatives

Thermal-induced dimerization cyclization of ethyl N-(styrylcarbamoyl)acetate derivatives has been investigated, leading to 4-hydroxy-2(1H)-pyridone-3-carboxamide derivatives with good yields in diphenyl ether on 200–210 °C. Ethyl N-(styrylcarbamoyl)acetate derivatives readily provided the intermolecular cyclization products 4-hydroxy-2(1H)-pyridone-3-carboxylates on reflux in xylene. In addition, several related 3-acetyl-4-hydroxy-5-phenylpyridin-2(1H)-ones have been prepared. It provided an efficient preparation of 4-hydroxy-2(1H)-pyridone-3-carboxamide derivatives.     

Structure of N-(1-silatranylmethyl) and N-(trimethoxysilyl-methyl) derivatives of nitrogen-containing heterocycles according to data of NMR, IR, and UV spectroscopy

The ¹H, ¹³C, ¹⁵N, and ²⁹Si NMR, IR, and UV spectra of N-(1-silatranylmethyl) and N-(trimethoxysilylmethyl) derivatives of nitrogen heterocycles have been studied. The dependence and interrelation of the chemical shifts of ²⁹Si and ¹⁵N nuclei of the silatranyl group in the spectra of N-(1-silatranylmethyl)-substituted nitrogen heterocycles are determined by the nature of the heterocyclic system. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1857–1865, December, 2006.