Synthesis of diversely 1,3,5-trisubstituted pyrazoles via 5-exo-dig cyclization

5-Exo-dig cyclocondensation of alk-3-yn-1-ones with hydrazines, in the presence of montmorillonite K-10, provides an effective method with a high atom economy for the synthesis of diversely 1,3,5-trisubstituted pyrazoles. The microwave-accelerated reaction proceeds in the absence of solvent and leads to 5-benzyl substituted pyrazoles with good yields (72-91%). The regiochemistry of the process was confirmed by the X-ray crystallographic structure determination of 1-(2-fluorophenyl)-5-(4-methylbenzyl)-3-phenyl-1H-pyrazole.     

Influence of various spices on acrylamide content in buckwheat ginger cakes

The aim of this work was to study the effect of various spices (cloves, cinnamon, allspice, white pepper, anise, star anise, coriander, fennel, nutmeg, cardamom, vanilla, and ginger) on acrylamide formation in buckwheat ginger cakes. The spices were characterised by their free radical scavenging activity and applied to formulation of the buckwheat ginger cakes in the same portions. After baking, the acrylamide content was determined by LC/ESI-MS-MS. The results showed a reduction in acrylamide content of up to 23 % in the buckwheat ginger cakes with the addition of nutmeg, fennel, anise, or cloves. A decrease in acrylamide content from 5 % to 11 % was found in the buckwheat ginger cakes with vanilla, cardamom, white pepper, or ginger. By contrast, the acrylamide content in the buckwheat ginger cakes with cinnamon or coriander increased by up to 29 %. No change in the acrylamide content was observed in the buckwheat ginger cakes with star anise or allspice. Only a slight correlation between the di(phenyl)-(2,4,6-trinitrophenyl)iminoazanium (DPPH^·) free radical scavenging activity of the added spices and the final acrylamide content in the buckwheat ginger cakes (0.68) was observed. The final acrylamide content was probably influenced not only by the free radical scavenging activity of the spices added, but also by their chemical composition and the reactiveness of particular constituents with synergistic/antagonistic effect in the matrix studied.     

1-Fluorosilatrane synthesis from SiF4 complexes and its properties

A new method of 1-fluorosilatrane synthesis on the basis of silicon tetrafluoride complexes obtained from SiO₂ is offered. Chemical properties of 1-fluorosilatrane in reactions of nucleophilic substitution are investigated. It is shown that fluorine can be substituted by O-nucleophiles (lithium methoxide, isopropoxide and phenoxide) and C-nucleophile (lithium phenylacetylenide).     

Ce3+-doped crystalline garnet films – scintillation characterization using α-particle excitation

Scintillating properties of Ce³⁺-doped (Lu,Y) aluminum garnet single crystalline films (SCF) were investigated. Thin SCF films of thickness between 1 and 30 μm were grown by a liquid phase epitaxy (LPE) method in various fluxes. The α-particle excitation (mainly 5.4857 MeV line of ²⁴¹Am) of pulse height spectra is used to measure scintillation response of SCF, especially peak of those α-rays which are totally absorbed in the films. Detailed studies and evaluation of scintillation measurements of large sets of Ce³⁺-doped SCF (Lu,Y) aluminum garnets showed that at present time (i) YAG:Ce SCF have comparable scintillation properties as YAG:Ce single crystals, especially their N_phels photoelectron yields are the same while (ii) scintillation properties of LuAG:Ce SCF do not reach those of LuAG:Ce single crystal.     

Direct formylation of 2-pyridone core of 3-N-methylcytisine via Duff reaction; synthesis of 9-enyl, 9-ynyl and 9-imino derivatives

The first direct synthesis of 3-N-methyl-9-formylcytisine via electrophylic formylation is described. It is established, that Vilsmeier-Haack and Gatterman variants of this reaction are unsuccessful in the case with 3-substituted (-)-cytisine derivatives, but Duff procedure (with hexamethylenetetramine in trifluoroacetic acid) gives a possibility to obtain the target pseudo aromatic aldehyde with the 69% yield. Convenient precursors for [4 + 2]- or [3 + 2]-cycloaddition reactions are obtained by means of condensation of synthesized 3-N-methyl-9-formylcytisine with acetone, nitromethane and phosphorous ylides with yields from 70 to 87%. Alternative aprroach to alkenyl products and to 9-alkynyl-3-methylcytisine is realized using the Heck and Sonogashira cross-coupling reactions of methyl vinyl ketone, cyclohexenone or trimethylsilylacetylene with 9-bromo-3-methylcytisine (55, 70 and 60% accordingly). It is shown, that interaction of 3-N-methyl-9-formylcytisine with hydroxylamines leads to corresponding nitrone (93%) and oxime (70%). All individual compounds are isolated by column chromatography and completely characterized on the basis of NMR spectroscopy data.     

A stereoselective total synthesis of the HCl salts of mycestericins F,G and ent-F

The total synthesis of the HCl salts of two natural sphingolipid-related amino acid derivatives, mycestericins F 4 and G 5 together with unnatural ent-4·HCl, starting from the four crucial scaffolds 6, 8, 9, 11 and utilizing the Wittig reaction to build the C₂₀ backbone, has been achieved. The selection of selective functional group interconversions accompanied with suitable protection–deprotection protocols in the coupling products 20 and 34 gave the desired structures.     

Liquid chromatography of synthetic polymers under critical conditions of enthalpic interactions 4: Sample recovery

Reduced sample recovery is a frequent feature of LC of macromolecules under critical conditions of enthalpic interactions (LC CC). Several methods of assessment of LC CC sample recovery are compared. A novel approach is based on an online combination of the. The LC CC column with a noninteractive SEC column. It provides not only the amount but also the molar mass of the eluted/withheld polymer. The procedure was tested with poly(methyl methacrylate), bare silica gel column packings, and “critical eluent” tetrahydrofuran/toluene. It was shown that macromolecules with higher molar masses were preferentially trapped within the LC CC column packing so that the eluted part of the sample was no longer representative. The incomplete polymer elution can make the LC CC polymer analyses susceptible to significant experimental errors.     

Preconcentration of Cr(III) and total Cr in waters for flame AAS in a flow-through electrochemical/sorption cell

Chromium in water samples is determined by flame atomic absorption spectrometry (AAS) after the preconcentration of Cr(III) species on activated alumina at pH 7 in a flow system coupled on-line to the AAS instrument. The total Cr concentration is determined after the electrochemical reduction of chromate ions to Cr(III) which are preconcentrated together with the original Cr(III) species in the sample. Both the reduction and the sorption are carried out in a combined cell containing a porous electrode, a layer of the sorbent and the counter electrode in series. The porous electrode is made of glassy carbon particles coated with gold. Tap, river and synthetic sea water samples were analyzed with this method. The detection limits are 0.5 ng/ml and 250 ng/ml for 500 ml and 1 ml sample solution, respectively.