Synthesis of D-Glucose-based Azacrown Ethers with Phosphinoxidoalkyl Side Chains and Their Application to an Enantioselective Reaction

Five chiral -D-glucose-based monoaza-15-crown-5 ethers with phosphinoxidoalkyl side chains of one to five carbon atoms (5a–e)have been synthesised. The cation binding ability of the new lariat ethers was evaluated bythe picrate extraction method. The substituents at the nitrogen atom were not a major influenceon the cation extraction ability of the azacrown ether; the compounds showed, however, a significant asymmetric induction as phase transfer catalysts in the Michael addition of2-nitropropane to chalcone (95% ee).     

“Comment” on the Reply to the Paper “On the Elber–Karplus Reaction Path-Following Method and Related Procedures”

The flaws in the Reply [1] to our paper [2] have been pointed out. Elber and Karplus (EK) have not disproved our irrefutable global statement that the energy average cannot be minimized which rebuts the theoretical background of EK-type calculations. Another statement of ours has shown that even a curve for which the average energy is locally minimal for all directional perturbations in the sense of classical variational calculus cannot be identical with the reaction path (RP) defined as a steepest descent path (SDP). EK found an error in the early preprint of our theoretical paper [3] and because of this error they qualified our correct variational statement as false for all the SDPs consisting of a straight line each. Mixing global and variational arguments, EK refuted our criticism in a logically incorrect manner. In this Comment we prove that both of our earlier statements invariably remain in force and the criticism included in those has been as well-established and solid as was before.     

Synthesis of alkyl α- and β-<Emphasis Type="SmallCaps">d</Emphasis>-glucopyranoside-based chiral crown ethers and their application as enantioselective phase-transfer catalysts

Chiral monoaza-15-crown-5-type lariat ethers annelated to alkyl 4,6-O-benzylidene-α- and β-d-glucopyranosides have been synthesized. These macrocycles generated significant asymmetric induction as phase-transfer catalysts in a few two-phase reactions. The catalytic effect of the lariat ethers with methoxy, ethoxy, and i-propoxy substituents on C-1 of the sugar unit in both α and β positions was compared. In liquid–liquid two-phase reactions, the nature and position of the substituents did not have much effect. The α-anomers were somewhat more efficient in terms of enantioselectivity than the β forms. In asymmetric Darzens condensations, in the epoxidation of trans-chalcone, in the Michael addition of β-nitrostyrene and diethyl acetamidomalonate, and in the reaction of 2-benzylidene-1,3-indandione with diethyl bromomalonate, maximum enantioselectivities of 73, 94, 78, and 72%, respectively, were obtained in presence of glucopyranoside-based lariat ethers as catalysts.     

Green chemical syntheses and applications within organophosphorus chemistry

Application of the microwave (MW) technique offers many advantages in organophosphorus syntheses. Reluctant reactions may take place on MW irradiation. In most cases, MWs make the reactions more efficient in respect of rate, selectivity and yield. The benefits are shown via representative examples. MW irradiation may replace a catalyst, or simplify catalytic systems. The synthesis of catalysts incorporating heterocyclic P-ligands is also discussed. Where it was relevant, structural chemical details were also provided.     

Biological UV dosimeters in quality control of tanning tubes

Although according to the International Radiological Protection Association-International Non-Ionizing Radiation Committee recommendation (1991) the use of sunbeds for cosmetic purposes is not recommended, tanning devices are used widely. Ten different types of commercially available sunbed tubes have been studied using a uracil biological UV dosimeter, and three of them were analyzed in detail. Dimerization effectiveness of the tubes was measured directly, whereas efficiency of erythema induction was calculated weighting the emission spectra by the Commission Internationale de l'Eclairage erythema action spectrum. The data obtained demonstrate that quality control of sunbed tubes has to include not only the determination of the UV doses administered but also the assessment of the health risk due to the UVB and UVA components of the lamp. A method of quality control using the uracil biological dosimeter was elaborated, and the estimation of the "acceptable" exposure time was checked/controlled on 15 volunteers by assessing individually the erythema induction threshold. A correct classification of the sunbed tubes is proposed by characterizing the erythema induction versus DNA-damaging effectiveness of tubes.     

Structure of aqueous solutions of tetraethylammonium chloride investigated by positron annihilation and ultrasonic methods

The structure of aqueous solutions of tetraethylammonium chloride was investigated using compressibility and density measurements and positron annihilation methods. The experimental results are different from those obtained earlier for systems where hydrophobic hydration dominates, although some evidences for formation of cage-like hydrates in liquid phase were observed. The results are interpreted, among others, in terms of competition among different hydrates of the tetraethylammonium cations, hydration of chloride anions, and formation of ionic pairs.     

Refractive index behavior of SiO2-P2O5 glass in optical fiber application

The refractive index of SiO₂-P₂O₅ glass prepared by a modified chemical vapor deposition method is measured using an interference microscope. It is found that the refractive index in bulk form increases linearly at 9.5×10^-4 (mol.%)^-1 as the P₂O₅ concentration increases. It is also found that quenching at extremely high speed reduces the refractive index over 2 mol.% P₂O₅. The wavelength dispersion of the refractive index dn/dλ is constant up to 5 mol.% P₂O₅ producing a refractive index difference of 5×10^-3 compared with fused silica. Consequently, this glass materials is thought to be suitable for wide band-width optical fiber applications.     

Oriented crystal growth model explains the formation of titania nanotubes

We discuss the formation mechanism of titania nanotubes synthesized by the hydrothermal method. On the basis of a comprehensive analysis of TEM, HRTEM, FT-Raman, and N(2) adsorption data, we point out some major shortcomings of the currently accepted trititanate sheet rollup mechanism. We suggest that a novel formation mechanism, oriented nanotube crystal growth from nanoloop seeds, can explain the experimental findings better than the ones proposed so far.     

In situ shear investigation of the Synperonic A7-water system by small-angle X-ray scattering and freeze fracture

A shear cell was constructed in two variants for simultaneous small-angle X-ray scattering and freeze fracture. Using this cell, the changes in the layer structure and the domain formation of the Synperonic A7-water system were investigated under shear. The reconstructions of both the layer and domain structures were not observed in the steady state after 1 h (following a 2 h long shear period). Destruction of the lamellar arrangement and formation of aggregates occurred during the stress. It was concluded that the tixotropic behavior originates rather from the change of the domain structure with a typical size range of microm than from the changes of the inner structure of domains with lamellar arrangement.     

Solution-phase parallel synthesis of a pyridinium pyrazol-3-olate inner salt library using a three-component reaction

We present here the discovery of a novel, versatile, multicomponent reaction leading to various 4-[4-(pyridinium-1-yl)-2,5-dioxo-2,5-dihydro-1H-pyrrol-3-yl]-2H-pyrazol-3-olate inner salts. The structure of the unusual zwitterionic inner salts was elucidated, and the scope of the novel reaction was investigated. After rapid optimization, the reaction was adapted to parallel synthesis, and an 800-membered compound library was produced.