Pd (II)‐catalyzed vinyl addition polymerization of novel functionalized norbornene bearing dimethyl carboxylate groups

Three novel functionalized polynorbornenes (PNB) with pendant dimethyl carboxylate group (carboxylates—acetate, propionate, and butyrate) are synthesized as a vinyl‐type with a palladium (II) catalyst in high yield. The effects of size of substitutents, molar ratio of monomer to catalyst, solvent polarity, reaction time, and temperature on the polymerization of exo‐norbornene dimethyl propionate were systematically investigated. The low molar ratio and temperature, as well as high polarity of solvent, and long reaction time, are favorable for the enhancement of the monomer conversion, especially, the solvent have an obvious effect on the catalyst activity. The resulting poly(cis‐norbornene‐exo‐2,3‐dimethyl carboxylates) (PNB‐dimethyl carboxylates) show good solubility in common organic solvent and high thermal stability up to 360 °C. The glass transition temperature was detected by DMA at 331, 324, and 318 °C for acetate, propionate, and butyrate, respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3391–3399, 2007     

Aza Diels—Alder reactions of methyl trifluoropyruvate sulfonyl- and phosphorylimines with 1,3-dienes

2-Trifluoromethyl-substituted 1,2,3,6-tetrahydro-2-pyridyl carboxylates were synthesized in one step by the aza Diels—Alder reactions of methyl trifluoropyruvate sulfonyl- and phosphorylimines with 1,3-dienes.     

Simultaneous determination of alkylphenol ethoxylates and their biotransformation products by liquid chromatography/electrospray ionisation tandem mass spectrometry

Reversed-phase LC-MS/MS is used to determine major estrogenic alkylphenol ethoxylates (APEOs) and their biotransformation products. It allows the simultaneous analysis of eight APEOs, alkylphenoxy carboxylates (APECs) and alkylphenols (APs) in sewage treatment plant (STP) effluents in the same extract after solid-phase enrichment on polymeric Oasis HLB. As precursor ions, [APEO + NH4]+, [APEC - H]- and [AP - H]- were monitored. Instrumental limits of detection (LOD) were 2-600 pg, corresponding to sample concentrations of 0.04-12 ng l(-1), without correction for overall method recoveries. Matrix-induced signal suppression during electrospray ionisation (ESI) and extraction as well as overall method recoveries were assessed and the suitability of deuterated surrogates as internal standards was evaluated.     

The inclusion of rhodium(II)α-methyl-cinnamate in β-cyclodextrin

The preparation and characterization of the 1:1 inclusion compound of rhodium(II) -methyl cinnamate in -cyclodextrin is reported. Evidence of inclusion was obtained from X-ray powder diffraction results, Raman, IR and UV-Vis spectroscopic studies and thermal analysis. Given the potential antitumor activity of the rhodium(II) carboxylate and its virtual insolubility in water, its inclusion in -cyclodextrin opens the possibility for its transference to the aqueous phase.     

Electronic structure of axially ligated rhodium carboxylates: π back-bonding revisited

Fenske-Hall molecular orbital calculations have been applied to a new, structurally isolable analog of the intermediate involved in catalytic rhodium carboxylate carbenoid transformations. Results from the structural characterization of axially ligated rhodium acetate phenylisonitrile complexes have been utilized in approximate molecular orbital calculations. The results from the calculations suggest that a significant degree of π back-bonding exists between the metal and isonitrile fragments which, by analogy, implies that π back-bonding should also exist in the rhodium carbenoid intermediate. Sensitivity of the Fenske-Hall method to the magnitude of π back-donation in these complexes was gauged through calculations involving different phenylisonitrile groups in which the π back-bonding ability was modulated through derivativization. The reliability of the Fenske-Hall method was evaluated through a comparison to a high-level calculation. Received: 13 December 1996 / Accepted: 18 March 1997     

新型单膦配位羧酸银配合物的合成、表征及其热稳定性的研究(英)

0 IntroductionIn recent years, silver carboxylates have attractedmany interests, mostly because they are promisingcandidates in the growth of metal thin films via metal-organic chemical vapor deposition (MOCVD) tech-niques. These sliver compounds show low light sensi-tivity and relatively high thermal stability. Several ex-amples of bisphosphine ligands coordinated silver car-boxlylates have been reported[1￣4].Monophosphine coordinated silver complexes areexpected to have better volatility,…     

Ring‐Opening Reactions of 3‐Aryl‐1‐benzylaziridine‐2‐carboxylates and Application to the Asymmetric Synthesis of an Amphetamine‐Type Compound

Nucleophilic ring‐opening reactions of 3‐aryl‐1‐benzylaziridine‐2‐carboxylates were examined by using O‐nucleophiles and aromatic C‐nucleophiles. The stereospecificity was found to depend on substrates and conditions used. Configuration inversion at C(3) was observed with O‐nucleophiles as a major reaction path in the ring‐opening reactions of aziridines carrying an electron‐poor aromatic moiety, whereas mixtures containing preferentially the syn‐diastereoisomer were generally obtained when electron‐rich aziridines were used (Tables 1–3). In the reactions of electron‐rich aziridines with C‐nucleophiles, S_N2 reactions yielding anti‐type products were observed (Table 4). Reductive ring‐opening reaction by catalytic hydrogenation of (+)‐trans‐(2S,3R)‐3‐(1,3‐benzodioxol‐5‐yl)aziridine‐2‐carboxylate (+)‐trans‐ 3c afforded the corresponding α‐amino acid derivative, which was smoothly transformed into (+)‐tert‐butyl [(1R)‐2‐(1,3‐benzodioxol‐5‐yl)‐1‐methylethyl]carbamate((+)‐ 14 ) with high retention of optical purity (Scheme 6).     

Synthesis and Characterization of Diphenyltin(IV) Dicarboxylates Containing Germanium

Twelve new germanium substituted diphenyltin dipropionates with the general formula (R¹GeCHR²‐CHR³COO)₂SnPh₂ where R¹ = N(CH₂CH₂O)₃, (C₆H₅)₃ and (CH₃C₆H₄)₃, R² = H, CH₃, C₆H₅, p‐CH₃C₆H₄, p‐CH₃OC₆H₄, p‐ClC₆H₄, and R³ = H, CH₃ have been synthesized by the reaction of diphenyltin oxide with a germanium substituted propionic acid. All the compounds were characterized by elemental analysis, IR, multi‐nuclear (¹H, ¹³C, ¹¹⁹Sn) NMR and Mössbauer spectroscopies as well as mass spectrometry. The in vitro antibacterial activity of selected compounds is also reported.     

不同种类羧酸钠对草酸钙结晶过程中晶相的影响

采用X射线衍射法研究了水溶液中不同种类羧酸钠对尿结石主要成份草酸钙结晶的影响，这些羧酸钠分别为含有一、二、三和四个羧基的羟基乙酸钠（NaGly）、酒石酸钠（Na2Tart）、柠檬酸钠（Na3Cit）和EDTA二钠盐（Na2EDTA）.结果表明，随着羧酸钠浓度的增加，草酸钙的晶相均发生规律性的变化：从最稳定的一水草酸钙（COM），到不稳定的二水草酸钙（COD），最后转化为次稳定的三水草酸钙（COT）.不同结构羧酸钠抑制COM生长、促进COD生成的顺序为:Na3Cit >Na2Tart >Na2EDTA >NaGly.该结果将为临床上选择防结石药物提供新的思路.     

Simulation of mesogenic diruthenium tetracarboxylates: Development of a force field for coordination polymers of the MMX type

A classical molecular mechanics force field, able to simulate coordination polymers (CP) based on ruthenium carboxylates (Ru₂(O₂CR_eq)₄L_ax) (eq = equatorial group containing aliphatic chains, L_ax= axial ligand), has been developed. New parameters extracted from experimental data and quantum calculations on short aliphatic chains model systems were included in the generalized AMBER force field. The proposed parametrization was evaluated using model systems with known structure, containing either short or long aliphatic chains; experimental results were reproduced satisfactorily. This modified force field, although in a preliminary stage, could then be applied to long chain liquid crystalline compounds. The resulting atomistic simulations allowed assessing the relative influence of the factors determining the CP conformation, determinant for the physical properties of these materials. © 2013 Wiley Periodicals, Inc.