A new, fast and efficient synthesis of 3-aryl indenones: intramolecular cyclization of 1,3-diarylpropynones in superacids

1,3-Diarylpropynones were cleanly converted to the corresponding 3-arylindenones in various superacidic media. This new, simple, one-pot reaction proved to be efficient (yields up to 95%) and very fast (reaction time less than 30 min).     

The fixed point property in ordered sets of width two

We consider the fixed point property (FPP) in an ordered set of width two (every antichain contains at most two elements). The necessary condition of the FPP and a number of equivalent conditions to the FPP in such sets is established. The product theorem is proved, as well.     

Determination of thallium and lead in cadmium salts by anodic stripping voltammetry with addition of surfactants to suppress the cadmium peaks

Conditions have been found which make possible the determination of thallium and/or lead in cadmium and its salts without preliminary separation. The electrochemical activity of the cadmium, which usually interferes in the determination of thallium, is inhibited by the addition of 0.01% of polyethylene glycol of M.W. 4000. Thallium is determined by electrolysis at ?0.74 V vs. SCE, in 0.1M EDTA solution: 10^?1M thallium can be determined in the presence of 0.1M cadmium, while copper and lead at 10^?2M and 10^?5M respectively do not interfere. Lead is determined in 0.1M acetic acid containing 0.1% cetyltrimethylammonium bromide (CTAB). The addition of CTAB shifts the cadmium peak, as well as the optimum deposition potential for cadmium, to more negative values, making it possible to determine lead in the presence of cadmium as long as the deposition potential lies in the range between ?0.50 and ?0.56 V vs. SCE. Lead can be determined in the presence of ten times as much thallium.     

Synthesis, crystal structure, and nonlinear optical behavior of beta-unsubstituted meso-meso E-vinylene-linked porphyrin dimers

[structure: see text] A vinylene-linked porphyrin dimer, with no substituents at the beta-positions, has been synthesized by CuI/CsF promoted Stille coupling. In the crystal structure of this dimer, the C(2)H(2) bridge is twisted by 45 degrees relative to the plane of the porphyrins. The absorption, emission spectra, and electrochemistry reveal substantial porphyrin-porphyrin pi-conjugation. The triplet excited-state absorption spectrum of this dimer makes it suitable for reverse saturable absorption at 710-900 nm.     

Beiträge zur Chemie der Silicium-Schwefel-Verbindungen. 46 [1]. 29Si-NMR-chemische Verschiebungen von Trialkoxysilylthioderivaten der Permethylpolysilane

Contributions to the Chemistry of Silicon-Sulphur Compounds. 46. ²⁹Si-N.M.R. Chemical Shifts of Trialkoxysilylthio Derivatives of Permethylpolysilanes ²⁹Si-N.M.R. chemical shifts of trialkoxysilythio derivatives of permethylpolysilanes of the two series: α, ω-(RO)₃SiS(SiMe₂)_nSSi(OR)₃, n = 2, 3, 4, 6 and 1-(RO)₃SiS(SiMe₂)_nMe, n = 2, 4; R = i-Pr, t-Bu and also ³¹C-NMR shifts are given. The relationship of ²⁹Si-NMR chemical shift from the netto charge at the silicon atom q(Si) which value has been corrected according to the Sandorfy C quantum-chemical model is discussed. The greater reduction of the electron density at silicon in compounds with Si? X bond (X = S, P, Cl) has been explained by a conjugation of the lone of sulphur with the Si? X bonding pair.     

C-Acylation of Electron-Excess Heterocycles by Isocyanatophosphoric Acid Dichlorides

Abstract

Isocyanatophosphoric acid dichlondes was used for introduction of phosphorus-containing groups at electron-excess heterocycles. Hetaryl containing dichlorophosphates, convenient starting material for synthesis for wide set of derivatives, were prepared by C-acylation with this reagent.     

Magnetic resonance study of annealed and rinsed N-doped TiO2 nanoparticles

Nanoparticles of nitrogen-modified TiO₂ (N-doped TiO₂) calcined at 300°C and 350°C, have been prepared with and without water rinsing. Samples were characterized by x-ray diffractrometry (XRD) and optical spectroscopy. The electron paramagnetic resonance (EPR) spectra from centers involving oxygen vacancies were recorded for all samples. These could be attributed to paramagnetic surface centers of the hole type, for example to paramagnetic oxygen radicals O^?, O₂ ^? etc. The concentration of these centers increased after water rising and it further increased for samples annealed at higher temperature. Additionally, for samples calcined at 300°C, and calcined at 350°C and rinsed, the EPR spectra evidenced the presence of magnetic clusters of Ti³⁺ ions. The photocatalytic activity of samples was studied towards phenol decomposition under unltraviolet-visible (UV-Vis) irradiation. It was found that, in comparison to the starting materials, the rinsed materials showed increased photocatalytic activity towards phenol oxidation. The light absorption (UV-Vis/DRS) as well as surface Fourier transform infrared/diffuse reflectance spectroscopy (FTIR/DR) studies confirmed a significantly enhanced light absorption and the presence of nitrogen groups on the photocatalysts surfaces, respectively. A significant increase of concentration of paramagnetic centers connected with oxygen vacancies after water rising has had an essential influence on increasing their photocatalytic activity.      

Purified oxygen- and nitrogen-modified multi-walled carbon nanotubes as metal-free catalysts for selective olefin hydrogenation

Oxygen- and nitrogen-functionalized carbon nanotubes (OCNTs and NCNTs) were applied as metal-free catalysts in selective olefin hydrogenation. A series of NCNTs was synthesized by NH₃ post-treatment of OCNTs. Temperature-programmed desorption, N₂ physisorption, Raman spectroscopy, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy were employed to characterize the surface properties of OCNTs and NCNTs, aiming at a detailed analysis of the type and amount of oxygen- and nitrogen-containing groups as well as surface defects. The gas-phase treatments applied for oxygen and nitrogen functionalization at elevated temperatures up to 600 °C led to the increase of surface defects, but did not cause structural damages in the bulk. NCNTs showed a clearly higher activity than the pristine CNTs and OCNTs in the hydrogenation of 1,5-cyclooctadiene, and also the selectivity to cyclooctene was higher. The favorable catalytic properties are ascribed to the nitrogen-containing surface functional groups as well as surface defects related to nitrogen species. In contrast, oxygen-containing surface groups and the surface defects caused by oxygen species did not show clear contribution to the hydrogenation catalysis.