Unique solvent effects on selective electrochemical fluorination of organic compounds

Recent studies on solvent effects on electrochemical partial fluorination are reviewed. At first, the historical background and some problems of electrochemical fluorination in organic solvents like acetonitrile (MeCN) are briefly mentioned. Ethereal solvents like dimethoxyethane (DME) and a mixture of DME and MeCN were found to improve both the yield and current efficiency for electrochemical fluorination since these solvent systems effectively suppress anode passivation and overoxidation of fluorinated products once formed during the electrolysis. It was also found that DME stabilizes radical cationic intermediates of 4-arylthio-1,3-dioxolan-2-ones and 3-phenylthiophthalide leading to α-fluorination while dichloromethane (CH₂Cl₂) destabilizes them leading to fluorodesulfurization. On the other hand, imidazolium ionic liquids and liquid fluoride salts like Et₄NF·4HF and Et₃N·5HF exhibited similar effects to CH₂Cl₂. Selective fluorination of hardly oxidizable phthalide was also achieved using a combination of two kinds of ionic liquids (imidazolium triflate and liquid fluoride salts).     

Side effects in measurements of selectivity coefficients of solid state ion selective electrodes

The influence of various factors such as solubility, the oxidation of the membrane, and the contamination of the solution, on the experimental values of the selectivity coefficients of solid state sulphide ion selective electrodes is discussed. A new method for the evaluation of very small selectivity coefficients, based on the addition of reagents forming complexes or insoluble salts with the main ion, is proposed. By means of this method, selectivity coefficients for silver, copper, cadmium and lead ion selective electrodes have been determined, which are in far better agreement with thermodynamic values than those described in the literature.     

Asp746 to Glycine Change May have a Greater Influence than Cys751 to Serine Change in Accounting for Ligand Selectivity between EGFR and HER-2 at the ATP Site

Summary We have carried out up to 8.0 ns molecular dynamics simulation on the ATP-bound complexes of EGFR and HER-2 (homology model) receptor kinase domains to explore the possible consequences of amino acid residue changes in or close to the ATP site that might provide insights for selectivity of these kinases towards ATP site inhibitors. The simulation results show the formation of a channel under Thr766 following the movement of the side chain of Gln767 away from the hinge in EGFR. In HER-2, a similar movement of Gln799 occurs, but a simultaneous movement of Arg784 towards the hinge region occurs that tends to close the channel. The movement of Arg784 in HER-2 appears to result from the absence of an anchoring residue like Asp746 in EGFR, which has been changed to Gly778 in HER-2. In EGFR, this Arg784 is held away from the hinge region by interaction with Asp746, thereby leaving the channel open. This might be an important contributory factor to differences in selectivity of the ligands between the two kinases, probably more so than the conservative change of Cys751 of EGFR to serine in HER-2 at the ATP site.     

3,3,3-Trifluoro-<Emphasis Type="Italic">N</Emphasis>′-(3-trifluoromethylphenyl)-1,2-propanediamine and its <Emphasis Type="Italic">N</Emphasis>-mono-and <Emphasis Type="Italic">N,N</Emphasis>-dicarboxyethyl derivatives: synthesis,protolytic and complexation properties

3,3,3-Trifluoro-N′-(3-trifluoromethylphenyl)-1,2-propanediamine (5) was synthesized by the reaction of 2-diazo-1,1,1-trifluoro-3-nitropropane or 3,3,3-trifluoro-1-nitropropene with 3-aminobenzotrifluoride followed by the reduction of the nitro group. The Michael 1,4-addition of diamine 5 to acrylic acid occurs only at the N(1) atom and affords N-mono-or N,N-dicarboxyethyl derivatives 6 and 7, depending on the reactant ratio. Protolytic equilibria 5–7 in aqueous solutions were studied by pH-potentiometry and UV spectroscopy. Only the aliphatic amino group can be protonated in an aqueous solution, while the aromatic amino group remains unprotonated even in 12 M HCl. The stability constants of transition metal (Cu²⁺, Ni²⁺, Zn²⁺) complexes with ligands 5–7 were determined by pH-potentiometric titration. The stability of the complexes and selectivity of the ligands toward Cu²⁺ ions increase with an increase in the number of N-carboxyethyl groups. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2465–2469, November, 2005.     

Role of Ion exchange in permeation processes

The single ion transport of transition metal ions like Cu²⁺, Co²⁺, Ni²⁺ and Zn²⁺ were carried out through the H⁺ and alkali metal ion forms of Nafion membrane. These studies showed that the ion exchange selectivity coefficient of the permeating ion had an effect on its transport process. It was found that the diffusion coefficient values (D) were directly proportional to the selectivity coefficient (K). This shows that the initial stage of permeation is governed by ion exchange process (effect of K on D).     

STUDY ON PREPARATION OF INORGANIC COMPOSITE MEMBRANE AND ITS PROPERTIES FOR HYDROGEN PERMEATION

IntroductionDevclopmcntoftcchniqucsforthcscparationofgascousmixturesisofgrcatimportancetochemicalindustries.Rccentadvanccsinceramicmaterialprocessinghavcstimulatedtheeffortstodcvclopccramicormctallicmcmbrancsforgasseparation.Suchmembraneswouldbesuitableforthescparationsathightemperatureatx`hichthcx`ellcstablishedorganicpol}mermcmbranescannotfunctionButmostcommercialceramicmembranesxvhichcanbcobtainedinmarkctaremicroporous(porediamcterfromO.ItoloPm)whereseparationmcchanismisgovcrncdbyKnudscnd…     

Elution order in gas chromatography

The retention behavior of a heterogeneous group of solutes has been examined on seven different stationary phases under isothermal and temperature-programmed conditions. Both ΔH_v (enthalpy of solute vaporization from the stationary phase) and ΔS_v (entropy of solute vaporization from the stationary phase) values were determined for each solute – stationary phase combination under isothermal conditions. Both program rate and carrier gas velocity were shown to affect solute elution order. Unless these and other experimental factors discussed are controlled, column equivalency studies based on solute elution order have dubious value.     

化学反应的选择性和金属有机化学

本文是对旨在提高合成效率的化学反应选择性和金属有机化学关系的综述,按金属有机化合物的基元反应进行讨论。     

Universal system for liquid stationary phase classification on the basis of thermodynamical data

Summary Equations modifying Rohrschneider's relationship between I and thermodynamical characteristics values are derived. Polarity in chromatography is discussed as a possibility of stationary phases or absorbents to enter into intermolecular interactions and is determined on the basis of the partial molar free energies of solution (G) of six test substances. A simple method for the calculation of stationary phase polarity in terms of G from retention indices and McReynolds constants is given. Equations are presented for the calculation of stationary phase selectivity utilizing G data tabulated for selected test substances. The thermodynamical basis of selecting a reference phase for a unified system expressing the selectivity of stationary phases which can also be applied for adsorbents is suggested. The energy equivalent to an index unit, G_i.u., is discussed.     

Ion-exchange selectivity of a network calixarene-containing polymer obtained by the template synthesis on Na<Superscript>+</Superscript>, K<Superscript>+</Superscript>, and Ba<Superscript>2+</Superscript> matrices

The ion-exchange equilibrium in network polymers obtained from cis-2,8,14,20-tetraphenyl-4,6,10,12,16,18,22,24-octahydroxycalix[4]arene by template synthesis on cations Na⁺, K⁺, and Ba²⁺ as matrices was studied. The selectivity coefficients of ion exchanges Ba²⁺-H⁺, Na⁺-H⁺, K⁺-H⁺, Na⁺-K⁺, and Na⁺-NH₄ ⁺ were determined. The template synthesis enhanced the affinity of the polymers to matrix-forming cations by 6–8 kJ mol⁻¹. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1919–1922, August, 2005.