Synthesis of a New Class of Highly Functionalized Phosphorus Ylides Containing Heterocyclic Compounds

The zwitterionic intermediate generated from the reaction of triphenylphosphine with electron deficient acetylenic compounds was trapped by various NH acids. The synthesis resulted in a new class of highly functionalized heterocyclic compounds. Some of the reactions produced E and Z isomers. And the stability and transformation of them were studied by dynamic ¹H NMR and density functional theory (DFT) calculations.     

A TRICHLORO-BRIDGED DIRUTHENIUM (II,III) COMPLEX: PREPARATION,PROPERTIES AND X-RAY STRUCTURE OF TRI(-μ-CHLORO) DICHLOROCARBONYLTRIS (TRIPHENYLPHOSPHINE)DIRUTHENIUM(II,III)

Abstract

The triply chloro-bridged binuclear complex [Ru₂Cl₅(CO)(PPh₃)₃]·CH₂Cl₂, (PPh₃ = triphenylphosphine), M_r = 1279.23, prepared from the precursor compound [RuCl₃(PPh₃)₂DMA]·DMA (DMA = N,N′-dimethylacetamide) and crystallizes in the monoclinic space group P2₁/c. The structure was solved from 6994 independent reflections for which I > 3σ(I) by Patterson and difference Fourier techniques and refined to a final R = 0.042. The complex is formed by two Ru atoms bridged through three chloride anions. One Ru atom is further coordinated to two non-bridging Cl atoms and a triphenylphosphine ligand, whereas the other is bonded to two PPh₃ ligands and a carbon monoxide molecule. The presence of Ru^III was confirmed by EPR data. The absence of an intervalence charge-transfer transition (IT) in the near-infrared spectrum suggests that the binuclear complex is of a localized valence type. The IR spectrum shows a ν_CO band at 1964cm^? and ν_Ru-Cl bands at 328, 280 cm^?1, corresponding to chlorides at terminal positions and 250, 225 cm^?1 for the bridged ones. Two redox processes, Ru^II/Ru^II (E_1/2 = -0.29 V) ← Ru^II/Ru^III ← (E_1/2 = 1.19 V) Ru^III/Ru^III, were observed by cyclic voltammetry.     

Towards an easy carbon dioxide reduction in aqueous solution

Abstract

The homogeneous hydrogenation of carbon dioxide into formate anion has been investigated in aqueous solution, using water soluble ruthenium(1I)-phosphine (meta-monosulphonated triphenylphosphine, TPPMS; and 1,3,5-triaza-7-phosphaadamantane, PTA) complexes as catalysts. These reactions take place in amine free medium under mild conditions, bicarbonate anion is more active than carbon dioxide in the reduction. The initial turnover frequenc of the reduction increases with increasing H₂ pressure, as it was observed in situ by C and 'H NMR spectroscopy. High pressure FT-IR were used to find evidence for the formation of the catalytically active ruthenium hydride species.     

Dynamic 1H NMR investigation along with a theoretical study around the C–C and C = C bonds in a particular phosphorus ylide

In the present work, the dynamic ¹H NMR effects were investigated at variable temperatures within a particular phosphorus ylide involving a 2‐benzoxazolinone around the carbon–carbon single bond and also partial carbon–carbon double bond in two Z‐ and E‐rotational isomers. Activation and kinetic parameters including ΔH^≠, ΔG^≠, ΔS^≠ and E_a were determined in accord with the dynamic ¹H NMR data for three rotational processes. In addition, theoretical studies based upon rotation around the same bonds were investigated using ab initio and DFT methods at the HF/6‐31G(d,p) and B3LYP/6‐31G(d,p) levels of theory. Theoretical activation and kinetic parameters including ΔH^≠, ΔG^≠, ΔS^≠ and E_a were calculated at 298 K and experimental temperatures for five rotational processes. These results (experimental and theoretical), taken together, indicate that the rotational energy barrier around the C = C double bond was considerably high and the observation of the two rotational isomers was impossible (seen as a single isomer) at the high temperatures, in this case rotation around the C = C bond was too fast on the NMR time scale. When the temperature was relatively low, the rate of rotation was sufficiently slow; therefore, observation of the two Z‐ and E‐isomers was possible. In addition, calculations at the HF/6‐31G(d,p) level of theory showed very favorable results in agreement with the experimental data on rotation around the C = C bond. While, B3LYP level using the 6‐31G(d,p) basis set was provided the reasonable data for the restricted rotations around the C–C and C–N single bond. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis,reactions, and biological study of some new thienopyrimidine derivatives as antimicrobial and anti‐inflammatory agents

Pyrimidine and thienopyrimidine derivatives play a very important role in organic chemistry because of their wide applications as bioactive compounds with multiple biological activities. However, a literature survey revealed that the merger of different groups in the thieno[2,3‐d]pyrimidine heterocyclic ring enhances its antibacterial, antifungal and anti‐inflammatory activities. This encouraged us to prepare a new series of thieno[2,3‐d]pyrimidine heterocyclic compounds and to test them as antimicrobial and anti‐inflammatory agents. These compounds have shown remarkable activity toward fungi, bacteria, and inflammation. Thus, these compounds have been prepared by the chloroacylation of 5‐amino‐4‐phenyl‐2‐(p‐tolylamino)thieno[2,3‐d] pyrimidine‐6‐carboxamide ( 4 ) using chloroacetyl chloride under neat condition to afford the target compound ( 6 ), which was used as precursor for the synthesis of a number of bioactive compounds. Thus reaction of the chloromethylpyrimidine derivative ( 6 ) with triphenylphosphine in dry benzene gave the corresponding ((4‐oxo‐9‐phenyl‐7‐(p‐tolylamino)‐3,4‐dihydropyrimido[4′,5′:4,5]thieno[2,3‐d]pyrimidin‐2‐yl)methyl) triphenylphosphonium chloride ( 7 ). Compounds 8a – 8c and 9a – 9c were obtained by the reaction of 7 with some selected aromatic aldehydes and ketones in methanol and sodium methoxide under Wittig reaction condition. The structures of the all new synthesized compounds were established on the basis of their analytical and spectral data (IR, ¹H NMR, ¹³C NMR, and MS).     

Rational Design 2-Hydroxypropylphosphonium Salts as Cancer Cell Mitochondria-Targeted Vectors: Synthesis,Structure, and Biological Properties

It has been shown for a wide range of epoxy compounds that their interaction with triphenylphosphonium triflate occurs with a high chemoselectivity and leads to the formation of (2-hydroxypropyl)triphenylphosphonium triflates 3 substituted in the 3-position with an alkoxy, alkylcarboxyl group, or halogen, which were isolated in a high yield. Using the methodology for the disclosure of epichlorohydrin with alcohols in the presence of boron trifluoride etherate, followed by the substitution of iodine for chlorine and treatment with triphenylphosphine, 2-hydroxypropyltriphenylphosphonium iodides 4 were also obtained. The molecular and supramolecular structure of the obtained phosphonium salts was established, and their high antitumor activity was revealed in relation to duodenal adenocarcinoma. The formation of liposomal systems based on phosphonium salt 3 and L-α-phosphatidylcholine (PC) was employed for improving the bioavailability and reducing the toxicity. They were produced by the thin film rehydration method and exhibited cytotoxic properties. This rational design of phosphonium salts 3 and 4 has promising potential of new vectors for targeted delivery into mitochondria of tumor cells.     

稀土-2,6-吡啶二甲酸-氧化三苯基膦配合物的合成及其荧光性质

稀土离子尤其是Sm,Eu,Tb,Dy因为其良好的荧光性能而得到了广泛的研究和应用[1,2]。吡啶二甲酸和氧化三苯基膦这两种配体有较大范围的共轭π键,在近紫外区又都有较宽的吸收带和较强的吸收峰,与稀土离子配位后可以构成有效的能量传递体系,将它们在近紫外区吸收的能量有效地传递给     

三苯基磷对PTG材料照相性能的影响

本文研究了三苯基磷(PPh₃)对以AgSt为银源的亲水型PTG材料照相性能的影响:PTG材料的感光度随PPh₃用量不同而变化,PPh₃用量相对较少时,感光度随PPh₃用量增加而提高;PPh₃用量增加到一定程度,感光度达到极大值;进一步增加PPh₃用量,感光度反而随PPh₃用量增加而下降.据分析结果推测,在PPh₃用量较少时,PPh₃的作用主要是打开AgSt二聚体的八元环而生成一种中间配合物,该中间体对热显影有促进作用;在PPh₃用量较多时,PPh₃的作用主要是与AgSt作用生成稳定的四元环配合物,该配合物对热显影有抑制作用.PPh₃的引入也会影响光敏元中潜影的形成效率,有利于提高感光度.     

Structural characterization and preliminary decomposition study of four unsymmetrically substituted nickel dithiocarbamate complexes

Single-crystal X-ray structures of four nickel dithiocarbamate complexes, the homoleptic mixed-organic bis-dithiocarbamates Ni[S₂CN(isopropyl)(benzyl)]₂, Ni[S₂CN(ethyl)(n-butyl)]₂, and Ni[S₂CN(phenyl)(benzyl)]₂, as well as the heteroleptic mixed-ligand complex NiCl[P(phenyl)₃][(S₂CN(phenyl)(benzyl)], were determined. A slightly distorted square-planar nickel coordination environment was observed for all four complexes. The organic residues adopt conformations to minimize steric interactions. Steric effects also may determine puckering, if any, about the nickel and nitrogen atoms, both of which are planar or nearly so. A trans-influence affects the Ni-S bond distances. Nitrogens interact with the CS₂ carbons with a bond order near two; the other substituents on nitrogen display transoid conformations. There are no strong intermolecular interactions, consistent with prior observations of the volatility of nickel dithiocarbamate complexes. A preliminary thermolysis study of the homoleptic species results in production of 1?:?1 nickel sulfide phases, indicating the potential utility of these species as “single-source” precursors.     

Synthesis of n,n′-biquinolines by a coupling reaction of bromoquinolines using organonickel(0) complexes

Tris(triphenylphosphine)nickel(0) (A) and a zerovalent pyridine–nickel complex (B) have been used as reagents for the coupling reaction of 3-, 6- and 8-bromoquinolines: 3,3′-, 6-6′- and 8,8′- Biquinolines were obtained in quantitative yields when A was used as the coupling reagent. B gave always a mixture of the n,n′ -biquinoline and substitution products. A mechanism can be outlined to explain the coupling reaction of bromoquinolines using zerovalent nickel complexes.