Temperature dependence of the substrate selectivity in the hydroxylation of alkylbenzenes in the H2O2−H2SO4 system

The substrate selectivity in the hydroxylation of methylbenzenes in the H₂O₂−H₂SO₄ (70 wt.%) system was studied at 15–55 °C. The activation entropy correlates with the basicity of the arenes, while the substrate selectivity and activation enthalpy correspond both with the basicity and ionization potentials of ArH. We concluded that the structure of the reaction transition state is intermediate between a charge transfer complex and σ-complex. L. M. Litvinenko Institute of Physical Organic and Coal Chemistry, National Academy of Sciences of Ukraine, 70 R. Lyuksemburg ul., Donetsk 340114, Ukraine. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 35, No. 1, pp. 39–43, January–February, 1999.     

Topology of the electron density of multicenter bonding in the anion TCNE2 2−

For TCNE₂ ^2? the role of bond paths in the electron density is emphasized to show that the anion contains multicenter bonding interactions across 4 central carbon atoms conferring inherent stability to it, consistent with experimental, and theoretical studies of other authors.     

Kinetics of decomposition of the liquid phase of the ternary system LiOH-H2O2-H2O in the presence of the solid phase of Li2O2 · H2O

The kinetics of decomposition of hydrogen peroxide in the liquid phase of the ternary system LiOH-H₂O₂-H₂O was studied in the presence the solid phase of Li₂O₂·H₂O and without it. The main kinetic parameters of the processes studied were determined.     

Synthesis ofβ-glycosides of n-acetylglucosamine in the presence of HgI2

The use of HgI₂ as catalyst in the synthesis oftrans-glycosides of N-acetylglucosamine is described. Using this catalyst, -glycosides of N-acetylglucosamine with aglycons of different structures and lyophilicities have been synthesized. The possibility of performing oligosaccharide synthesis has been demonstrated.     

Influence of NO on the Reduction of NO2 with CO over Pt/SiO2 in the Presence of O2

Reduction of NO2 with CO in the presence of NO and excess oxygen, a model mixture for flue gas, over a 0.1% Pt/SiO2 catalyst was studied. The related reaction mechanisms, such as oxidation of CO and NO, were discussed. It was found that there was a narrow temperature window （180-190 ℃） for the reduction of NO2 by CO. When the temperature was lower than the lower limit of the window, the reduction hardly occurred, while when the temperature was higher than the upper limit of the window, the direct oxidation of CO by O2 occurred and thereby NO2 could not be effectively reduced by CO. The presence of NO shifted the window to higher temperatures owing to the inhibition effect of NO on the activation of O2 on Pt, which made it possible to reduce NO2 by CO in flue gas.     

Diffusion of linear paraffins in silicalite studied by the ZLC method in the presence of CO2

The diffusion behavior of C₄–C₁₀ n-alkanes in silicalite-1 has been investigated by using the Zero Length Column method. The diffusivities derived from measurements at different purge rates with different purge gases confirming intracrystalline diffusion control. Data are compared with results reported in the literature for MFI zeolites. The diffusivities were found to be consistent and agree well with data previous obtained by ZLC. However, these data showed a remarkable disagreement with other reported techniques (PFG-NMR, QENS and Permeation). The eventual influence of carbon dioxide (CO₂) adsorption on diffusion properties of n-alkanes in silicalite was also investigated. For this purpose, a series of experiments was performed involving hydrocarbons mixed with CO₂. Data were obtained at 303 K and flow rates between 20 and 80 mL/min. The presence of CO₂ does not seem to influence the intracrystalline transport rate of the investigated light hydrocarbons (n-C₄ and n-C₆). On the other hand, the situation for n-C₈ and n-C₁₀ is more complex. The diffusivity values are higher compared to the previously reported values.     

Alkylation of 2-Sulfanylbenzoxazole with α-Iodoketones in the Absence of Bases

Reaction of 2-sulfanylbenzoxazole with 1-iodopropan-2-one, 2-iodo-1-phenylethanone, and 2-iodo-1-(thiophen-2-yl)ethanone without solvent and bases afforded bis(benzoxazol-2-yl)disulfonium derivatives in a single preparative stage. The reaction proceeds as a domino-process and includes the alkylation of a sulfanyl group of benzoxazole, the reduction of iodoketone with hydrogen iodide, the oxidation of 2-sulfanylbenzoxazole to disulfide, the alkylation of disulfide atoms of sulfur, and the formation of triiodideanions. The yield of disulfonium derivatives increases twice in the presence of equimolar amount of iodine.     

Behaviour of β2-microglobulin in the electrical double layer of the mercury/solution interface

β₂-Microglobulin (β₂-m) is a small globular protein (12000 Da) which exists as a monomer in numerous body fluids. Data published on the electrochemical behaviour of β₂-m are scarce. In this paper an attempt was made to ge more information on the structure of the double layer at mercury/solution interface in the presence of β₂-m. Using phase selective ac polarography the capacitive current-potential (C-E) curve was analysed as the function of various β₂-m concentration, pH of medium, temperature, denaturation agent concentration etc. The data obtained are discussed particularly from the aspect of folding/unfolding state of the protein studied.     

The Unusual Spectrum of the Mixture of Tin-octabutoxy Naphthalocyanine and SnCl2 in CH2Cl2

The Q-band position of tin-centered 5, 9, 14, 18, 23, 27, 32, 36-octabutoxy 2, 3-phthalocyanine(SnNc(OBu)8) exhibits dramatic red-shift as mixed with SnCl2 in CH2Cl2.     

An infrared study of the stretching modes of the water molecules in ZnF2·4H2O

The IR spectra of ZnF₂·4H₂O and its deuterated analogues are reported at ambient and liquid-nitrogen temperatures. The OH and OD stretching and bending vibrations of the water molecules are analysed in detail. The two types of water molecules give rise to different absorption peaks in the OH and OD stretching regions in samples that contain isotopically dilute HDO groups. The strongly hydrogen-bonded water molecules H₂O(1) and H₂O(4) show four broad OH and OD stretching modes at lower frequencies, while the weaker hydrogen-bonded ones H₂O(2) and H₂O(3) give rise to four narrow bands at higher frequencies. The ν_OD frequencies of isotopically dilute HDO groups correlate very well with the known R(H---F) and R(H---O) distances in the crystals and the assignment of these modes was done on this basis. It was also found that the ratio ν_OH/ν_OD decreases with decreasing values of R(H---O) or R(H---F) in ZnF₂·4H₂O.     

Study on the Deactivation Kinetics of Pd（PPh3）2Cl2 in the Monocarbonylation of Benzyl Chloride

The deactivation kinetics of Pd(PPh3)2Cl2 in the monocarbonylation of benzyl chloride to synthesize phenylacetic acid is studied in this paper. Solid 1-(2-pyridylazo)-2-naphthol (PAN) is used as the colouring agent, and the concentration of Pd(PPh3)2Cl2 in the system is measured through absorptiometry. The result shows that the optimum condition of the chromogenic reaction between Pd2+ and PAN is: 0.5 ml of 0.04% PAN added to 10 ml of Pd2+ solution (1.0×10-6-2.0×10-5 mol/L), and heated in a constant temperature water bath at 40℃ for about 30 min, with pH of the solution being about 3.0. The molar coefficient of absorption is 1.384×104 L/(mol·cm); the orders of the hydrolytic reaction to the concentration of Pd(PPh3)2Cl2, PPh3, phenylacetic acid and NaOH are 0.5, minus 0.8, 2 and 1.2, respectively. The activation energy (E) of the hydrolytic reaction is 75.59 kJ/mol, and the pre-exponential factor is 1.68×1012.     

Asymmetric Arrangement of Monolayer in the Multilayer Films of 2-Hydroxy-4,4''''-dihexyloxy-azobenzene

IntroductionConstructionoffunctionalmolecularunitsintostruc turallywell definedsupramolecularassemblieshasattract edgreatattentionduetotheirpotentialapplicationsincomplexelectronicstructuresandmoleculardevices .1 5Amongthevariousfunctionalorganicmolecules ,azoben zenederivativeshavebeenwidelystudiedbecauseoftheirinterestingphotoresponsivebehavior .6 11Extensivestudieshaveshownthatsuitablydesignedazobenzenederivativescanformlongrangeorderedarrangementoftwo orthree dimensionalmolecularlatticeat…     

Synthesis of (VO)2P2O7 catalystsvia exfoliation-reduction of VOPO4·2H2O in butanol in the presence of ethanol

The exfoliation-reduction of VOPO₄·2H₂O in l-butanol oriso-butanol alone, and in a l-butanol/ethanol oriso-butanol/ethanol mixture, were conducted. Although all precursors were composed of a lamellar compound with intercalated alcohol molecules, VOHPO₄·0.5H₂O was formed when the exfoliation-reduction process was carried out in the mixed alcohol. All precursors transformed to a single phase of (VO)₂P₂O₇ under the reaction conditions forn-butane oxidation, but the crystallinity of (VO)₂P₂O₇ was different. The catalyst synthesized iniso-butanol/ethanol was well crystalline (VO)₂P₂O₇, and exhibited higher selectivity to maleic anhydride than that synthesized iniso-butanol alone for then-butane oxidation.     

Mechanochemical Reaction of Aromatic Ketones and Aldehydes in the Presence of Zn-ZnCl2

The solvent-free reactions of aromatic ketones and aldehydes in the presence of Zn-ZnCl2 were performed with the aid of high-speed vibration mill, Retsch MM200 mixer mill and Retsch RM100 mortar grinder to give pinacol coupling and reduction products in varying yields.     

Determination of Dopamine in the Presence of Ascorbic Acid on the IrO2-Ta2O5 Type DSA Electrode

IrO2Ta2O5 (70%: 30%, molar ratio) electrodes (ITEs) were prepared by the thermal decomposition method. Typical “mud-cracked” surface and surface enrichment of Ta were observed. The determination of dopamine (DA) was carried out in the presence of ascorbic acid (AA). The detection limit of DA was 5~10 5 mol/L without the interference of AA.     

Quantum chemical modeling of the cis-trans isomerization of the allyl ligand in Ni(η3-C3H5)2 in the presence of norbornadiene

Quantum chemical (DFT/PBE) modeling of the cis-trans isomerization of the allyl ligand in bis(η³-allyl)nickel in the presence of norbornadiene revealed that the type of coordination of the norbornadiene ligand affects the energy parameters of its isomerization. The Gibbs energies of activation of the rate-limiting step for different isomerization pathways range from 23.7 to 27.8 kcal mol^?1.     

Manifestation of the Even–Odd Effect in the Spectral Properties of Solvated Electron and in the Probability of Positronium Formation in Alcohols

A change in the energy E _max of the solvated electron, which corresponds to the maximum intensity of its optical absorption spectrum in the homologous series of alcohols seems to be alternating in character. The effect is retained upon elevation of pressure up to 2 kbar but disappears in alcohols frozen at 77 K. Probably, the effect also holds for amines. The alternating character of variation is also observed for the intensity Y ₁ of the narrow components of the angular spectrum of -photons generated upon positron annihilation in alcohols and normal alkanes. The nature of alternation of E _max is associated with the mutual elimination of electric fields induced by the dipole moments of two neighboring CH₂ groups in each solvent molecule, including also the molecules forming the solvation shell of an excess electron. That fact that the E _max value correlates to Y ₁ led to the conclusion that Y ₁, rather than the intensity I ₃ of the long-lived component of the annihilation time spectrum generally used for the purpose, more adequately characterizes the positronium formation probability.     

Challenges in measuring the δ13C of the soil surface CO2 efflux

The δ13C of the soil surface efflux of carbon dioxide (δ13CRS) has emerged as a powerful tool enabling investigation of a wide range of soil processes from characterising entire ecosystem respiration to detailed compound-specific isotope studies. δ13CRS can be used to trace assimilated carbon transfer below ground and to partition the overall surface efflux into heterotrophic and autotrophic components. Despite this wide range of applications no consensus currently exists on the most appropriate method of sampling this surface efflux of CO2 in order to measure δ13CRS. Here we consider and compare the methods which have been used, and examine the pitfalls. We also consider a number of analysis options, isotope ratio mass spectrometry (IRMS), tuneable diode laser spectroscopy (TDLS) and cavity ring-down laser spectroscopy (CRDS). δ13CRS is typically measured using chamber systems, which fall into three types: closed, open and dynamic. All are imperfect. Closed chambers often rely on Keeling plots to estimate δ13CRS, which may not be appropriate without free turbulent air mixing. Open chambers have the advantage of being able to maintain steady-state conditions but analytical errors may become limiting with low efflux rates. Dynamic chambers like open chambers are complex, and controlling pressure fluctuations caused by air movement is a key concern. Both open and dynamic chambers in conjunction with field portable TDLS and CRDS analysis systems have opened up the possibility of measuring δ13CRS in real time permitting new research opportunities and are on balance the most suited to this type of measurement.     

Determination of the Amplification Factor for 2-Hydroxy-ethylperoxy Radicals in PERCA

Free radicals (HO?, HO2? and organic peroxy radicals RO2?) play a crucial role in atmospheric chemistry1,2. Accurate measurement of these species is important to understand the chemical processes in the atmosphere. Recently, a chemical amplify- cation tec…     

Rotational spectrum of SiC2 in the ν3 excited state

The rotational spectra of SiC₂ in the vibrationally excited states of the ring deformation mode (υ₃ = 1, 2) were observed in the frequency region of 140–400 GHz by using a source-modulated microwave spectrometer combined with a free space absorption cell. SiC₂ was produced in the cell by discharging a mixture of SiH₄, C₂H₂ and CO. Least-squares analysis of the observed spectral lines yielded the rotational constants and the centrifugal distortion constants precisely. Sextic, octic and decatic centrifugal distortion constants were required in the least-squares fit in order to get a good fit of the observed frequencies to those calculated within experimental errors. The inertial defects for the υ₃ = 1 state and the υ₃ = 2 state do not show a linear dependence on the vibrational quantum number. The quartic centrifugal distortion constants, Δ_JK, Δ_K and δ_K, are abnormally large, and show a large change on the vibrational states. These abnormal behaviours are interpreted in terms of a large amplitude motion of the ν₃ mode.