Polymeric Pd catalysts for the reduction of acetamidocinnamic acid azlactone and its solvolysis products

Pd complexes have been obtained from linear and cross-linked copolymers ofR,S-, R-, andS-1-(4-vinylphenyl)ethylamine (1) with styrene and divinylbenzene. Reduction of these compounds gave catalysts which were active in the reductive solvolysis of -acetaminocinnamic acid azlactone (2) and hydrogenation of the solvolysis products -acetamidocinnamic acid (ACA), its esters, and its 1-phenylethylamide. The catalysts showed no enantioselective properties in the reductive hydrolysis, but were more active than the catalyst obtained in the absence of the polymer (the monomeric analog). The use of polymeric catalysts has shown that, in reductive aminolysis, the chiral nucleophile plays the dominant part in determining the stereoselectivity of the reaction, rather than the chiral ligand of the catalytic complex. The polymer matrix stabilizes the low-valent state of the palladium in the complex. In the hydrogenation of ACA and its esters, the catalyst on the cross-linked polymer is much more active than its monomeric analog, but showed no enantioselectivity. Hydrogenation of acetamidocinnamic acidR-andS-1-phenylethylamides on a chiral Pd-polymer catalyst occurred with double asymmetric induction.Deceased.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 117912 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2368–2380, October, 1992.     

Experimental and Theoretical Studies of a Pulsed Microwave Excited Ar/CF4 Plasma

The present work deals with a pulsed microwave discharge in an Ar/CF ₄ gas mixture under a low pressure (1–10 mbar). The discharge chamber developed has a cylindrical geometry with a coupling window alternatively made of quartz or alumina. The setup allows one to investigate the plasma–wall interactions (here etching of the quartz window) and the ignition process of the pulsed microwave plasma. Microwave pulses with a duration of 50–200 s and repetition rate between 1 and 10 kHz are typical for the experiments. The space-time behavior of the fluorine number density in the discharge has been investigated experimentally by optical actinometry. The discharge kinetics is modeled using electron-transport parameters and rate coefficients derived from solutions of the Boltzmann equation. Together with the solution of the continuity and electron balance equations and the rate equations describing the production of CF _x (x=2, 3, 4) radicals and F atoms, a good agreement between experimental and theoretical data can be achieved.     

Manganese Catalysts for the Ozone-Assisted Oxidation of Volatile Organic Compounds: Effect of the Mn3+/Mn4+ Active Site Ratio on Catalytic Properties

Kinetics and Catalysis - The catalytic properties of supported Mn/carrier catalysts (carriers: Al2O3, SiO2, SiO2–Al2O3) in the ozone-assisted oxidation of volatile organic compounds (using...     

Condensation of 3,5-Dialkyltetrahydro-4H-thiopyran-4-ones with Formaldehyde

Russian Journal of General Chemistry - The reaction of 3,5-dimethyl- and 5-methyl-3-(2-propyl)tetrahydro-4H-thiopyran-4-ones with formaldehyde without or in the presence of 0.1–0.5 equiv....     

High-Selective Catalyst Based on Intermetallic Rh1In1 Particles for Nitrobenzene Hydrogenation

Kinetics and Catalysis - The catalytic performance of a bimetallic RhIn/SiO2 catalyst was studied in the liquid-phase hydrogenation of nitrobenzene. The formation of intermetallic Rh1In1...     

Coherent focusing of high harmonics: a new way towards the extreme intensities

We demonstrate analytically and numerically that focusing of high harmonics produced by the reflection of a few-femtosecond laser pulse from a concave plasma surface opens a new way to unprecedentally high intensities. The key features allowing the boosting of the focal intensity are the harmonics coherency and the small exponent of the power-law decay of the harmonics spectrum. Using similarity theory and direct particle-in-cell simulations, we find that the intensity at the focus scales as I(CHF) alpha a(3)(0)I(0), where a(0) and I(0) alpha a(2)(0) are the dimensionless relativistic amplitude and the intensity of the incident laser pulse. The scaling suggests that due to the coherent harmonic focusing (CHF), the Schwinger intensity limit can be reached using lasers with I(0) approximately 10(22) W/cm(2). The pulse duration at the focus scales as tau(CHF) alpha 1/a(2)(0) and reaches the subattosecond range.     

Relativistic Doppler effect: universal spectra and zeptosecond pulses

We report on a numerical observation of the train of zeptosecond pulses produced by the reflection of a relativistically intense femtosecond laser pulse from the oscillating boundary of an overdense plasma because of the Doppler effect. These pulses promise to become unique experimental and technological tools since their length is of the order of the Bohr radius and the intensity is extremely high proportional, variant 10(19) W/cm(2). We present the physical mechanism, analytical theory, and direct particle-in-cell simulations. We show that the harmonic spectrum is universal: the intensity of nth harmonic scales as 1/n(p) for n<4gamma(2), where gamma is the largest gamma factor of the electron fluid boundary, and p=3 and p=5/2 for the broadband and quasimonochromatic laser pulses, respectively.     

Specific features of the catalytic behavior of supported palladium nanoparticles in heterogeneous catalytic reactions

Specific features of the catalytic behavior of supported palladium nanoparticles were analyzed in terms of both the size of the particles and their interaction with the support. The influence of these factors on the activity and selectivity of palladium nanoparticles in carbon-carbon bond hydrogenolysis, hydrogenation of aromatic compounds, olefins, and acetylenes, hydrodechlorination, as well as complete oxidation of organic compounds was discussed. It was shown that the optimal nanoparticle size depends on the type of the reaction and also such factors as the nature of interaction between the nanoparticles and support, absorptivity of the substrates and catalytic reaction products, and electronic and crystal structure of the nanoparticles.     

Photocatalytic removal of nitrogen oxides from air on TiO<Subscript>2</Subscript> modified with bases and platinum

The efficiency of TiO₂ (Degussa P-25) modified with an alkaline admixture (urea, BaO), sulfuric acid, or platinum in the photocatalytic oxidation of NO (50 ppm) with a flowing 7% O₂ + N₂ mixture under UV irradiation in a flow reactor at room temperature and atmospheric pressure is reported. Because of the progressive blocking of active sites of the photocatalyst by the reaction products (NO₂, NO₃⁻), it is impossible to realize prolonged continuous removal of NO _x (NO + NO₂) from air without catalyst regeneration at elevated temperatures. The efficiency of the photocatalysts is characterized by specific photoadsorption capacity (SPC) calculated from the total amount of NO _x adsorbed during 2-h-long irradiation. Modification of TiO₂ with 5% BaO or 5% urea raises the SPC of the catalyst by a factor of 2–3. Presumably, this promoting effect is due to the basic properties of these dopants, which readily sorb NO₂ and NO₃⁻. A considerable favorable effect on SPC is also attained by adding 0.5% Pt to (5% BaO)/TiO₂. The SPC of the (0.5% Pt)/TiO₂ catalyst depends on the state of the platinum. The samples calcined in air at 500°C, which contain Pt⁺ and Pt²⁺, have an approximately 2 times higher SPC than unpromoted TiO₂ and ensure a much larger NO₂/NO ratio at the reactor outlet. Conversely, the samples reduced in an H₂ atmosphere at 200°C, whose platinum is in the Pt0 state, show a lower SPC than the initial TiO₂ and cause no significant change in the NO₂/NO ratio.