Synthesis of 4,4′-Bis[4-(2,5-dioxo-2,5-dihydro-1H-pyrroll-1-yl)-phenylcarbonylamino]-3,3′-dichlorodiphenylmethane and 1,4-Bis{2-[4-(2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl)-phenylcarbonyloxy]ethoxy}benzene

Russian Journal of Organic Chemistry - 4,4′-Bis[4-(2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl)phenylcarbonylamino]-3,3′-dichlorodiphenylme-thane has been obtained by the reaction of...     

(2)(∞)[Co{1,4-C6H4(CN)2}2{NTf2}2][SnI{Co(CO)4}3](2)--a 2D coordination network with an intercalated carbonyl cluster

Dark red transparent crystals of [Co{1,4-C(6)H(4)(CN)(2)}(2){NTf(2)}(2)][SnI{Co(CO)(4)}(3)](2) are obtained by reacting SnI(4), Co(2)(CO)(8) and 1,4-C(6)H(4)(CN)(2) in the ionic liquid [EMIm][NTf(2)] (EMIm: 1-ethyl-3-methylimidazolium; NTf(2): bis(trifluoromethylsulfonyl)imide). According to X-ray structure analysis based on single crystals, the title compound crystallizes in a triclinic manner and contains the novel (2)(∞)[Co{1,4-C(6)H(4)(CN)(2)}(2){NTf(2)}(2)] coordination network. This infinite 2D network is composed of Co(2+) ions that are planarily interlinked by four 1,4-dicyanobenzene ligands. As a non-charged 2D network, Co(2+) is furthermore coordinated by two [NTf(2)](-) anions. The (2)(∞)[Co{1,4-C(6)H(4)(CN)(2)}(2){NTf(2)}(2)] layers are stacked on top of each other with SnI[Co(CO)(4)](3) molecules intercalated in distorted cubic gaps between the layers. The title compound is furthermore characterized by energy dispersive X-ray (EDX) analysis, thermogravimetry (TG), infrared spectroscopy (FT-IR) and optical spectroscopy (UV-Vis).     

Thermodynamic Model for BiPO4(cr) and Bi(OH)3(am) Solubility in the Aqueous Na+–H+–\mathrm{H}_{2}\mathrm{PO}_{4}^{-}–\mathrm{HPO}_{4}^{2-}–\mathrm{PO}_{4}^{3-}–OH−–Cl−–H2O System

Prior to this study no data for the solubility product of BiPO₄(cr) or the complexation constants of Bi with phosphate were available. The solubility of BiPO₄(cr) was studied at 23±2?°C from both the over- and under-saturation directions as functions of a wide range in time (6–309 days), pH values (0–15), and phosphate concentrations (reaching as high as 1.0 mol?kg^?1). HCl or NaOH were used to obtain a range in pH values. Steady state concentrations and equilibrium were reached in <6 days. The data were interpreted using the SIT model. These extensive data provided a solubility product value for BiPO₄(cr) and an upper limit value for the formation of BiPO₄(aq). Because the aqueous system in this study involved relatively high concentrations of chloride, reliable values for the complexation constants of Bi with chloride were required to accurately interpret the solubility data. Therefore as a part of this investigation, existing Bi–Cl data were critically reviewed and used to obtain values of equilibrium constants for various Bi–Cl complexes at zero ionic strength along with the values for various SIT ion interaction parameters. Predictions based on these thermodynamic quantities agreed closely with our experimental data, the chloride concentrations of which ranged as high as 0.7 mol?kg^?1. The study showed that BiPO₄(cr) is stable at pH values <9.0. At pH values >9.0, Bi(OH)₃(am) is the solubility controlling phase. Reliable values for the Bi(OH)₃(am) solubility reactions involving Bi(OH)₃(aq) and $\mathrm{Bi}(\mathrm{OH})_{4}^{-}$ and the formation constants of these aqueous species are also reported.     

Synthesis of 2-methoxy-2-methyl-3-{6-[2-(5-methyl-2-phenyl-1,3-oxazol-4-yl)ethoxy]pyridin-3-yl}propanoic acid, a dual PPARα/γ agonist

Large quantities of an enantiomerically pure novel dual PPARα/γ agonist were required. Three routes were successfully developed to achieve this goal, with the chosen route utilized to deliver 40 g of material.     

2,4-Bis{[6-(2,2-dimethylpropyl)-3-ethyl-1,3-benzothiazol-2(3H)-yl­idene]methyl}cyclobutenediylium-1,3-­diolate

The title compound, C₃₄H₄₀N₂O₂S₂, adopts a trans conformation. The four conjugated Csp²—Csp² single and double bonds of the polymethinic moiety, which bridges both heterocyclic end groups and the central four-membered ring, display nearly equal bond lengths. The mol­ecule is nearly planar, with interplanar angles between the benzo­thia­zole end groups and the central four-membered ring of 6.9 (1) and 7.7 (1)°; the angle between the heterocyclic systems is 1.8 (1)°. The crystal packing involves π-stacking effects, with intermolecular C⃛C distances varying from 3.755 (3) to 3.991 (3) Å.     

Tris(pyrazolyl)borate half-sandwich complexes of trivalent uranium incorporating the [C8H6{SiiPr3-1,4}2]2− and [C8H4{SiiPr3-1,4}2]2− ligands

The reaction of UI₃ in THF with KTp^Me2 and the subsequent addition of [K₂(C₈H₆{SiⁱPr₃-1,4}₂)] or [K₂(C₈H₄{SiⁱPr₃-1,4}₂)] yields dark red [U(κ³-Tp^Me2)(C₈H₆{SiⁱPr₃-1,4}₂)] 1 and purple [U(κ³-Tp^Me2)(C₈H₄{SiⁱPr₃-1,4}₂)] 2, respectively. The ¹H NMR of 1 at room temperature suggests a rigid structure, whereas 2 is fluxional in solution on the NMR timescale. 1 is unreactive towards CO, CO₂ and MeNC under mild conditions; density functional calculations were used to compare the electronic and steric effects of the Tp^Me2 vs. Cp* ligands in mixed sandwich complexes of the type [U(L)(C₈H₆{SiH₃-1,4}₂)] (L = Cp* or (κ³-Tp^Me2)). On heating at 80 °C, 1 reacts with excess MeNC to yield [U(C₈H₆{SiⁱPr₃-1,4}₂)(κ²-dmpz)₂(η¹-CNMe)] 3. The structures of 1–3 have been determined by single crystal X-ray diffraction.     

Ferromagnetic interactions in a 1D alternating linear chain of π-stacked 1,3-diphenyl-7-(thien-2-yl)-1,4-dihydro-1,2,4-benzotriazin-4-yl radicals

X-ray studies show that 1,3-diphenyl-7-(thien-2-yl)-1,4-dihydro-1,2,4-benzotriazin-4-yl (6) adopts a distorted, slipped π-stacked structure of centrosymmetric dimers with alternate short and long interplanar distances (3.48 and 3.52 ?). Cyclic voltammograms of 7-(thien-2-yl)benzotriazin-4-yl 6 show two fully reversible waves that correspond to the -1/0 and 0/+1 processes. EPR and DFT studies on radical 6 indicate that the spin density is mainly delocalized over the triazinyl fragment. Magnetic susceptibility measurements show that radical 6 obeys Curie-Weiss behavior in the 5-300 K region with C=0.378 emu K mol(-1) and θ=+4.72 K, which is consistent with ferromagnetic interactions between S=1/2 radicals. Fitting the magnetic susceptibility revealed the behavior is consistent with an alternating ferromagnetic chain (g=2.0071, J(1) =+7.12 cm(-1), J(2) =+1.28 cm(-1)).     

Single crystal X-ray analysis of isomeric 2-(2,4,4-trimethyl-3,4-dihydro-2h-benzo[h]× chromen-2-yl)-1-naphthyl acetate and 3-(2,4,4-trimethyl-3,4-dihydro-2H-benzo[g]× chromen-2-yl)-2-naphthyl acetate

Single crystal X-ray structure characterization of isomeric 2-(2,4,4-trimethyl-3,4-dihydro-2H-benzo[h]chromen-2-yl)-1-naphthyl acetate (1) and 3-(2,4,4-trimethyl-3,4-dihydro-2H-benzo[g]chromen-2-yl)-2-naphthyl acetate (2) is described. Compound 1 crystallizes in the centrosymmetric monoclinic space group P2₁/c with all atoms situated in general positions. Isomeric compound 2 crystallizes in the centrosymmetric triclinic space group P-1 and its structure consists of two crystallographically independent molecules with all atoms located in general positions. In addition to intramolecular C-H??O bonding, 2 is involved in two intermolecular C-H??O interactions resulting in a one-dimensional H-bonded network.     

From an {Fe4S4}-cluster to {Fe2S2}- and {Fe3S}-carbonyls. Crystal structure of [Fe3S(CO)9]2−

We report the electrochemical and chemical synthesis of the first isolable iron carbonyls obtained directly from an {Fe₄S₄}-cluster and carbon monoxide: the structure of one product of chemical reduction, [Fe₃S(CO)₉]²⁻, had been determined by X-ray crystallography.     

基于{Er_2}和{Cu_2}单元构建的超分子网络(英文)

利用水热法成功合成了一个新颖的稀土-过渡金属有机骨架Er(pyba)3(H2O)2CuI(Hpyba=4-吡啶-3-苯甲酸),并通过元素分析、红外光谱、X-射线粉末衍射、单晶X-射线衍射及热分析等对其进行了表征。结构分析表明:2种不同的{Er2}和{Cu2}单元经配体连接形成一维链,这些一维链通过氢键和π-π堆积作用进一步连接形成三维超分子网络。     

二{2-{2-{9-乙基-6-[2-(8-羟基喹啉-2-基)乙烯基]咔唑-3-基}乙烯}-8-羟基喹啉}锌配合物的合成与荧光光谱特性

合成了新的N-乙基咔唑衍生物: 3,6-二[2-(8-羟基喹啉基)乙烯基]咔唑(4)及其锌配合物(5); 化合物4经质谱、红外光谱、核磁共振氢谱、元素分析表征其结构, 并测定了它的荧光光谱. 结果显示: 化合物4的荧光发射为蓝绿色光(500 nm), 其发射光谱随着溶剂极性的增大荧光光谱向长波方向移动(即发生红移); 同时, 考察了化合物5的荧光性质, 其荧光发光峰值为600 nm, 与2-甲基-8-羟基喹啉锌相比, 发生了明显的红移.     

Electrochemistry of Interaction Between Flavin Mononucleotide (FMN) and PM-17 as Antitumoral ε-Keggin Core Compound, \left[ {{\text{H}}_{ 2} {\text{Mo}}_{ 1 2}^{\text{V}} {\text{O}}_{ 2 8} \left( {\text{OH}} \right)_{ 1 2} \left( {{\text{Mo}}^{\text{VI}} {\text{O}}_{ 3} } \right)_{ 4} } \right]^{ 6- } at pH 7.5

In order to obtain a clue to the antitumor mechanism of $\left[ {{\text{Me}}_{ 3} {\text{NH}}} \right]_{ 6} \left[ {{\text{H}}_{ 2} {\text{Mo}}_{ 1 2}^{\text{V}} {\text{O}}_{ 2 8} \left( {\text{OH}} \right)_{ 1 2} \left( {{\text{Mo}}^{\text{VI}} {\text{O}}_{ 3} } \right)_{ 4} } \right]$ ·2H₂O (PM-17), the interaction of PM-17 with flavin mononucleotide (FMN) as a prosthetic group of the flavoprotein has been investigated by both polarographic analysis and isothermal titration calorimetry (ITC) technique at the physiological solution pH (7.5). The half-wave potential (?0.50 V vs. Ag/AgCl) of the d.c. polarogram for the quasi-reversible one-electron reduction of FMN was shifted by PM-17 toward a more positive potential with a resultant deviation from one-electron reduction to formally more than one-electron reduction waves. The PM-17 effect on the d.c. polarogram could be explained by a variety of FMN···(PM-17)_n (n > 0) aggregates with multiple conformations which was supported by the thermodynamic parameters (ΔH = ?29.7 kJ mol^?1, ΔS = ?28.2 J mol^?1 K^?1, ΔG = ?21.5 kJ mol^?1, and number of FMN in the binding with PM-17 (N) = 0.053 at 20 °C) estimated by the ITC technique. A large conformational change of the FMN domain by the FMN···(PM-17)_n aggregates is suggested to prevent the movement of the FMN centers into close proximity with nicotinamide adenine dinucleotide (NADH) with a resultant depression of the electron transport in NADH dehydrogenase.     

Structurally different divalent metallasiloxanes [Mg{O(Ph2SiO)2}2]-μ-(LiPy)-μ-{(LiPy)3(OH)(Cl)}], [Cr{O(Ph2SiO)2}-μ-(LiPy2)2], and [{O(Ph2SiO)2}Co{O(Ph2SiO)3)}-μ-(LiPy2)2] from Ph2Si(OH)2/2BuLi and the metal dichlorides

Three structurally different metallasiloxanes were formed from reactions between in situ generated suspensions of Ph₂Si(OH)₂/BuLi (1∶2) in tetrahydrofuran (THF) with, metal dichlorides MgCl₂·2THF, CrCl₂, or CoCl₂ followed by toluene/Py (Py=pyridine) work-up. The X-ray structures are reported for: [Mg{O(Ph₂SiO)₂}₂]-μ-(LiPy)-μ-{(LiPy)₃(OH)(Cl)] (1) incorporating two six-membered magnesiasiloxane rings and an MgLi₃O₃Cl cubane fragment, [{O(Ph₂SiO)₂}Co{O(Ph₂SiO)₃}-μ-(LiPy₂)₂] (2) with both six-and eight-membered cobaltasiloxane rings and [Cr{O(Ph₂SiO)₂}₂-μ-(LiPy₂)₂] (3) with two six-membered chromiasiloxane rings. Structure assembly in these cases is apparently dictated by the metal dichloride. The compound [{O(Ph₂SiO)₂}Mg{O(Ph₂SiO)₃}-μ-(CoClPy)₂]·Py (4) is formed from [{O(Ph₂SiO)₂}Mg{O(Ph₂SiO)₃}-μ-(LiPy₂)₂] and CoCl₂ (1∶2).     

Novel synthesis of substituted N-(3-aryl-1,8-naphthyridin-2-yl) and N,N′-bis(3-aryl-1,8-naphthyridin-2-yl)benzene-1,4-diamines and 2-(4-((3-aryl-1,8-naphthyridin-2-yl)amino)phenyl)isoindoline-1,3-diones and their biological evaluation

A straightforward and highly efficient series of new substituted 3-aryl-1,8-naphthyridine derivatives 3a–e, 4a–e, and 6a–e were synthesized. Condensation dissimilar quantities of 2-chloro-3-aryl-1,8-naphthyridine 1a–e with benzene-1,4-diamine 2 and sodium ethoxide refluxing in ethanol solvent yielded the compounds 3a–e and 4a–e. The 2-(4-((3-aryl-1,8-naphthyridin-2-yl)amino)phenyl)isoindoline-1,3-diones 6a–e were obtained by treatment of compounds 3a–e with phthalic anhydride 5 in refluxing N,N-dimethylformamide is described. All synthesized compounds evaluated for their antimicrobial activity. The structures of the compounds have been proven on the established of spectral (IR, ¹H NMR, and ¹³C NMR) data and elemental analyses. The reaction will be characterized by good efficacy, easy workup, simple purification of the products, and availability of catalyst.     

Ruthenium(II) nitro-nitroso-bis-{1-(alkyl)-2-(β-napthylazo)imidazole}: Synthesis,spectroscopy, electrochemistry and reactivity

Aquation of blue cis-trans-cis-[RuCl₂(β-NaiR)₂] (1) leads to the synthesis of solvento species, blue-violet cis-trans-cis-[Ru(OH₂)₂(β-NaiR)₂](ClO₄)₂ (2), [β-NaiR = C₁₀H₇-N=N-C₃H₂-NN, abbreviated as N,N′-chelator, R = Me] that have been reacted with NaNO₂ in warm EtOH resulting in violet dinitro complexes of the type, [Ru(NO₂)₂(β-NaiR)₂] (3). The nitrite complexes are useful synthons of electrophilic nitrosyls, and on triturating the dinitro compounds with cone. HClO₄ nitro-nitrosyl derivatives, [Ru(NO₂)(NO)(β-NaiR)₂]²⁺ (4) are isolated. The chemical oxidation of aqua complex (2) by excess aqueous eerie solution in 1 (N) H₂SO₄ leads to the spontaneous formation of a yellow colored species. The electrophilic behaviour of metal bound nitrosyl has been proved by reacting with a bicyclic ketone, camphor, containing an active methylene group and an arylhydrazone with an active methine group. The diazotization of the primary aromatic amines with a strongly electrophilic mononitrosyl complex in acetonotrile and dichloromethane solution was thoroughly studied. Electrocatalytic oxidation of benzyl alcohol was examined.     

Crystal Structure of Methyl 3- (2-chlorophenyl )-3- (5, 5-dimethyl-3-hydroxy-2-cyclohexene- 1-one-2-yl) propionate

1INTRODUCTIONInorganicsolidsupportsascatalystshavebeenwellstudied,becauseoftheirap-plicationsinorganicsynthese('~".Recently,wehavereportedtheKnoevenagelcon-densationcatalysedbyKF-Al,O,['i.Inthispaper,wediscussedthecrystalstruc-tureofthetitlecomPoundsynthesizedbythereactionof2-chlorobenzaldehydey5,5-dimethyl-1,3-cyclohexanedioneandisopropylidenemalonateinmethanolcatalyzedbyKF-Alzo,'Inordertoconfirmthestructureofthetitlecompound,theX-raycrys-tallOgraphicstudywascarriedout.2EXPER1MEN…     

Synthesis and Crystal Structure of a Novel Heptanuclear Ruthenium- and Sodium-containing Polyoxomolybdate [ {Na(H2O)3}2{Ru(dmso)3}2(MoO4)3]·3H2O

The title compound, [{Na(H2O)3}2{Ru(dmso)3}2(MoO4)3]·3H2O, has been obstructure was determined by single-crystal X-ray diffraction method. The crystal crystallizes in the triclinic system, space group P1 with a = 12.3333(3), b = 12.6289(3), c = 32.0284(14)(A), α =79.873(7), β = 87.549(9), y = 64.500(4)°, V = 4429.5(2) (A)3, Z = 4, Mr = 1358.85, Dc = 2.038g/cm3, F(000) = 2696 and μ = 1.874 mm-1. The compound contains a novel pentanuclear triangle bipyramidal core, [{ Ru(dmso)3 } 2(MoO4)3]2-, which consists of two { Ru(dmso)3 } 2+ fragments and three {μ2-MoO4}2- units. Furthermore, the dmso ligands bridge the pentanuclear [Ru2Mo3] core and two [Na(H2O)3]+ fragments together, forming a neutral heptanuclear ruthenium- and sodiumcontaining polyoxomolybdate.     

X-Ray Structural Analysis of Ethyl [2,2-dimethyl-6-(Δ2-thiazolin-2-yl)-4H-1,4-benzoxazin-3-one-4-yl]butyrate

With the aim of discovering new molecules with K⁺ channel modulating properties, we have synthesized analogues of cromakalim, an important molecule which shows specific affinity toward the K⁺ channels, by replacing the benzopyrane ring with a benzoxazine moiety. As a part of this study, we have synthesized and characterized, in solution and in the solid state as well, the compound ethyl [2,2-dimethyl-6-(²-thiazolin-2-yl)-4H-l,4-benzoxazin-3-one-4-yl]butyrate (V). This compound exhibits in the solid state the following parameters: molecular formula C₁₉H₂₄N₂O₄S, triclinic, space group , M_w = 376.5, a = 12.581(3) Å, b = 5.485(4) Å, c = 14.612(2) Å, = 91.85(2), = 108.9(3), = 82.04(4), V = 944.7 ų, Z = 2, d = 1.323 g·cm^–3. We describe here the synthesis and discuss the solid-state conformation of this new molecule; when tested on rat aorta ring precontracted with phenylephrine, the compound showed a concentration-dependent relaxation comparable to that measured for cromakalin taken as reference drug.     

Rearrangement of enol acetates of α-(3,5-dimethyl-1,2,4-triazol-1-yl)-2,4-dichloroacetophenone and α-(1,2,4-triazol-1-yl)-2,4-dichloropropiophenone

At 140 °C in acetic anhydride enol acetates of -(3,5-dimethyl-1,2,4-triazol-1-yl)-2,4dichloroacetophenone and -(1,2,4-triazol-1-yl)-2,4-dichloropropiophenone undergo 1,3and 1,5-rearrangement, respectively.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 182–184, January, 1995.     

Simultaneous LC?CMS?CMS Determination of HM30181A, [2-(2-{4-[2-(6,7-Dimethoxy-3,4-dihydro-1H-isoquinolin-2-yl)-ethyl]-phenyl}-2H-tetrazol-5-yl)-4,5-dimethoxyphenyl]amide, as a new P-Glycoprotein Inhibitor and Its Two Metabolites, M1 and M2, in Human Plasma: Application to a Pharmacokinetic Study

A simultaneous simple, rapid, and sensitive LC?CMS?CMS method was developed and validated for the determination of HM30181A, [2-(2-{4-[2-(6,7-dimethoxy-3,4-dihydro-1H-isoquinolin-2-yl)-ethyl]-phenyl}-2H-tetrazol-5-yl]-4,5-dimethoxy-phenyl]amide, as a P-glycoprotein inhibitor and its two metabolites, M1 and M2, in human plasma using docetaxel as an internal standard (IS). The analytes were extracted from 200???L of biological sample by liquid?Cliquid extraction using 1?mL of methyl-t-butyl ether. Chromatographic separation was carried on a Luna C8 column at 30???C with mobile phase consisting of distilled water with 0.1% formic acid and acetonitrile (75:25, v/v) at a flow rate of 0.7?mL?min^?1 for human plasma samples. The method was linear over concentration ranges of 0.5?C50, 0.1?C10, and 0.1?C10?ng?mL^?1 for HM30181A, M1, and M2, respectively, in human plasma. The values of coefficient variation for the assay precision were <12.5, <9.10, and <9.96% for HM30181A, M1, and M2, respectively, in human plasma. The values of accuracy were 93.0?C108, 94.7?C104%, and 95.7?C105% for HM30181A, M1, and M2, respectively, in human plasma. This method is simple, sensitive, and applicable for the pharmacokinetic studies of HM30181A and its metabolites in humans.