A density functional theory study on the electrocyclization of 1,2,4,6-heptatetraene analogues: converting a pericyclic to a pseudopericyclic reaction

A comprehensive B3LYP/6-31+G* study on the electrocyclization of 1,2,4,6-heptatetraene analogues was conducted. Starting from the cyclization of (2Z)-2,4,5-hexatrienal, a pericyclic disrotatory process favored by the assistance of a electron lone pair, we incorporated small modifications in its molecular structure to obtain a truly pseudopericyclic process. To this purpose electronegative atoms (fluorine and nitrogen) were added to give a more electrophilic character on the carbon atom which is attacked by the electron lone pair of the oxygen atom. The complete pathway for each reaction was determined, and changes in magnetic properties were monitored with a view to estimating the aromatization associated with each process. This information, together with the energetic and structural results, allowed us to classify the reactions as pseudopericyclic or pericyclic. Among all studied reactions only one was a truly pseudopericyclic process and another was a borderline case. The features of this unequivocally pseudopericyclic case were analyzed in depth.     

Evaluation of different quantitative approaches for the determination of noneasily ionizable molecules by different atmospheric pressure interfaces used in liquid chromatography tandem mass spectrometry: Abamectin as case of study

The liquid chromatography tandem mass spectroscopy residue determination of compounds without any acidic or basic centers such as abamectin has been investigated. Several approaches regarding the interface used and adduct formation have been compared. The low acidity of the hydroxyl groups only made deprotonation feasible using the atmospheric pressure chemical ionization (APCI) interface. To obtain sufficient sensitivity for residue analysis, the Ion Sabre APCI interface was necessary. However, the sensitivity attained was lower than for monitoring adducts in positive ion mode. Using electrospray ionization, different adducts with Na+, NH4+, and Li+ were tested and compared. The best results were obtained for the ammoniated adduct in electrospray ionization (ESI) because of its high sensitivity and the presence of several product ions with similar abundance. The highest sensitivity was reached using an in-source fragment as precursor ion, leading to a limit of detection (LOD) of 2 microg/L with low relative standard deviation. The relatively high abundance of other transitions allowed abamectin confirmation at concentrations close to the LOD (6 microg/L). Alkali ions were found to be a suitable alternative to determine and confirm abamectin at residue levels. The [M + Na]+ also presented various product ions with similar abundance, which allowed confirmation at LOD levels. However, this LOD was found to be almost four times higher than with [M + NH4]+ because of the poor sensitivity of the transitions obtained. Although the use of Li+ facilitated the fragmentation of the adduct [M + Li]+, with similar sensitivity to [M + NH4]+, this fragmentation preferentially generated only one product ion, which did not allow confirmation at concentration levels lower than 15 microg/L. The use of APCI for monitoring adducts was also feasible, but with less sensitivity. The sensitivity increased with the Ion Sabre APCI, although it was still five times lower than with ESI. Other adduct formers such as Co2+ and Ni2+ also were tested with unsatisfactory results.     

Preparation and properties of dinitrogen complexes of molybdenum and tungsten with trimethylphosphine as coligand : III. Synthesis and properties of cis-[W(N2)2(PMe3)4], trans-[W(C2H4)2(PMe3)4] and [M(N2)(PMe3)5] (M = Mo,W). The crystal and molecular structure of [Mo(N2)(PMe3)5]

The reduction of [WCl₄(PMe₃)₃] with dispersed sodium, under dinitrogen, gives cis-[W(N₂)₂(PMe₃)₄], while under ethylene trans-[W(C₂H₄)₂(PMe₃)₄] is obtained. The ethylene complex can also be prepared by displacement of the dinitrogen molecules in cis-[W(N₂)₂(PMe₃)₄] by ethylene at room temperature and pressure. Interaction of cis-[M(N₂)₂(PMe₃)₄] complexes (M = Mo, W), with PMe₃, under helium or argon, yields [M(N₂)(PMe₃)₅]. The molybdenum complex crystallizes in the orthorhombic space group Pnma, with a 22.063(6), b 12.106(4), c 9.745(4) Å. The Mo—P distance trans to the dinitrogen ligand (2.483(7) Å) is slightly longer than the average of the other four Mo—P bonds (2.460(5) Å).     

1,1,1,1-Tetrakis(o-fluorophenylamino)silane tris[titanium(IV) chloride]. Evidence for a new titanium cation [Ti2Cl7]+

Si(NHC₆H₄F-o)₄ · 3TiCl₄ (1) has been obtained from the disproportionation of (CF₃CH₂O)₃SiNHC₆H₄F-o and TiCl₄ in petroleum ether (40–60 °C) at –10 °C. The analytical (elemental analysis, molar conductance) and spectral (i.r., ¹H- and ¹⁹F-n.m.r.) data suggested that (1) behaves as [Si(NHC₆H₄F-o)₄ · Ti₂Cl₇]⁺ [TiCl₅]^–. The presence of these ions has been confirmed by characterising the products of metathetical reactions of (1) with R₄NX (R = Bu and Et; X = I and Br) and with AgNO₃. The data suggest the presence of a new titanium cation [Ti₂Cl₇]⁺.     

Analytical fractionation of aquatic humic substances and their metal species by means of multistage ultrafiltration

The molecular-size fractionation of aquatic humic substances (HS) and their metal species by means of a novel sequential-stage ultrafiltration (UF) device equipped with five appropriate ultramembranes (1, 5, 10, 50 and 100 kD) is described. First of all, the concentration dynamics of macromolecules, particulary HS, during five-stage UF and its subsequent washing step has been modelled. Based on these results, the fractionation of aquatic HS (from ground and bog water) by means of multistage UF has been optimized for an analytical scale (10 ml sample, 1 mg/ml HS, 10 ml washing solution, pH 6.0). The molecular size-distribution of selected aquatic HS (BOC 1/2 from the DFG-Versuchsfeld Bocholt, VM 5 from Venner Moor, Germany) studied by five-stage UF exhibited strong systematic influences of the procedure used for their isolation. The molecular-size distribution of HS obtained by on-line UF and gel permeation chromatography (GPC) showed a satisfactory agreement in the range 1–50 kD. Moreover, when interrupting multistage UF for > 48 h a slow transformation in the HS samples has been found as gradually additional HS fractions of < 1 kD have been formed. Besides unloaded HS molecules, the molecular-size distribution of freshly formed metal species of HS (1.0 mg metal/g HS of Al(III), Cd(II), Cu(II), Fe(III), Mn(II), Ni(II), Pb(II), Zn(II), each) has been characterized by multistage UF as a function of pH-value, degree of loading and complexation time. Metal determinations as carried out by flame AAS, showed that considerable metal fractions in HS especially are present in molecules > 50 kD, which seemed to be rather acid-inert. With complexation times of < 2 days a transient shift of the molecular size distribution of both HS and their metal species (e.g., Al(III), Fe(III) to higher values (> 10 kD) has been found.     

Flow analysis-vapor phase generation-Fourier transform infrared (FA-VPG-FTIR) spectrometric determination of nitrite

In this work, the coupling between flow analysis (FA)–vapor phase generation (VPG) and Fourier transform infrared spectrometry (FTIR) has been proposed as a novel and alternative strategy for the determination of nitrite. The analyte was transformed into the gaseous nitric oxide (NO) by on-line reaction with potassium iodide (KI) or ascorbic acid in acidic medium. The gaseous NO generated was transported by means of a N₂ gas carrier stream inside the IR gas cell and the corresponding FTIR spectrum was acquired in a continuous mode. The absorbance at 1876 cm⁻¹, corrected by a baseline established between 1879 and 1872 cm⁻¹ at a nominal resolution of 2 cm⁻¹, was selected as a measurement criterion. The effect of different spectroscopic and flow analysis experimental parameters, such as nominal resolution, number of scans, reducing agent and its concentration, acidic medium, reagents and sample flow rates, and the carrier gas flow rate on the analytical signal, and then in the figures of merit were initially evaluated by using a standard short path length (10 cm) IR gas cell. The optimization of the system was carried out by the univariate method. The main aims of this study were: (i) to investigate the on-line generation of gaseous nitric oxide in a continuous flow system, and (ii) the use of Fourier transform infrared spectrometry as an alternative and selective detector for the determination of nitrite. The proposed method was initially tested and applied for the determination of nitrite in samples with very high concentration of nitrite, such as frankfurters.     

Determination of organophosphorus and triazine pesticides in olive oil by on-line coupling reversed-phase liquid chromatography/gas chromatography with nitrogen-phosphorus detection and an automated through-oven transfer adsorption-desorption interface

A method is described for the simultaneous determination of organophosphorus and triazine pesticides in olive oil, whereby reversed-phase liquid chromatography (LC) is coupled to gas chromatography by means of an automated through-oven transfer adsorption-desorption (TOTAD) interface. The olive oil needs to be filtered only before it is loaded into the liquid chromatograph, where preseparation of the pesticide residues from the other olive oil components is carried out by using methanol-water as the eluant. The LC fraction containing the pesticides is automatically transferred to the gas chromatograph by using the TOTAD interface, which almost totally eliminates the solvent, so that water-sensitive detectors such as the nitrogen-phosphorus detector can be used. Detection limits range from 0.07 to 0.38 microg/L for organophosphorus pesticides and from 6.0 to 7.0 microg/L for triazines. The results were compared with those obtained by flame ionization detection.     

Synthesis and characterization of copper(II) and nickel(II) complexes of the Schiff base derived from 2-(2-aminophenyl)benzimidazole and salicylaldehyde

Summary Copper(II) and nickel(II) complexes with the Schiff base derived from 2-(2-aminophenyl)benzimidazole and salicylaldehyde, L, have been prepared. They are of the general types ML₂X₂ (M = Ni or Cu and X = Cl, Br, NO₃ or ClO₄) and NiL(NCS)₂.The compounds have been characterized by elemental analyses, magnetic measurements, e.s.r., electronic and i.r. spectra studies. The i.r. spectra suggest that the molecule, and not the anion, of the Schiff base is coordinated as a bidentate ligand with the metal ion. Possible structures for the complexes have been proposed.     

Contrasting behavior in azide pyrolyses: an investigation of the thermal decompositions of methyl azidoformate, ethyl azidoformate and 2-azido-N, N-dimethylacetamide by ultraviolet photoelectron spectroscopy and matrix isolation infrared spectroscopy

The thermal decompositions of methyl azidoformate (N3COOMe), ethyl azidoformate (N3COOEt) and 2-azido-N,N-dimethylacetamide (N3CH2CONMe2) have been studied by matrix isolation infrared spectroscopy and real-time ultraviolet photoelectron spectroscopy. N2 appears as an initial pyrolysis product in all systems, and the principal interest lies in the fate of the accompanying organic fragment. For methyl azidoformate, four accompanying products were observed: HNCO, H2CO, CH2NH and CO2, and these are believed to arise as a result of two competing decomposition routes of a four-membered cyclic intermediate. Ethyl azidoformate pyrolysis yields four corresponding products: HNCO, MeCHO, MeCHNH and CO2, together with the five-membered-ring compound 2-oxazolidone. In contrast, the initial pyrolysis of 2-azido-N,N-dimethyl acetamide, yields the novel imine intermediate Me2NCOCH=NH, which subsequently decomposes into dimethyl formamide (HCONMe2), CO, Me2NH and HCN. This intermediate was detected by matrix isolation IR spectroscopy, and its identity confirmed both by a molecular orbital calculation of its IR spectrum, and by the temperature dependence and distribution of products in the PES and IR studies. Mechanisms are proposed for the formation and decomposition of all the products observed in these three systems, based on the experimental evidence and the results of supporting molecular orbital calculations.     

Copper-assisted oxidation of catechols into quinone derivatives

Catechols are ubiquitous substances often acting as antioxidants, thus of importance in a variety of biological processes. The Fenton and Haber–Weiss processes are thought to transform these molecules into aggressive reactive oxygen species (ROS), a source of oxidative stress and possibly inducing degenerative diseases. Here, using model conditions (ultrahigh vacuum and single crystals), we unveil another process capable of converting catechols into ROSs, namely an intramolecular redox reaction catalysed by a Cu surface. We focus on a tri-catechol, the hexahydroxytriphenylene molecule, and show that this antioxidant is thereby transformed into a semiquinone, as an intermediate product, and then into an even stronger oxidant, a quinone, as final product. We argue that the transformations occur via two intramolecular redox reactions: since the Cu surface cannot oxidise the molecules, the starting catechol and the semiquinone forms each are, at the same time, self-oxidised and self-reduced. Thanks to these reactions, the quinone and semiquinone are able to interact with the substrate by readily accepting electrons donated by the substrate. Our combined experimental surface science and ab initio analysis highlights the key role played by metal nanoparticles in the development of degenerative diseases.

An antioxidant catechol transforms following intramolecular redox reactions into highly reactive oxygen species, a semiquinone and a quinone, on copper.