Micellar catalytic effects in the oxidation of methyl phenyl sulfide with hydrogen peroxide and the hydrogen peroxocarbonate anion

The kinetics and mechanism of the catalysis by ammonium hydrogen carbonate oxidation of methyl phenyl sulfide with hydrogen peroxide has been investigated. Using the classical pseudo-phase model of micellar catalysis, the basic parameters of the catalytic process have been determined: the binding constants of H₂O₂, the HCO ₄ ⁻ anion, and the substrate to the surface of the micelles, and also the second order rate constants for the oxidation of methyl phenyl sulfide in the micellar phase. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 5, pp. 281–287, September–October, 2006.     

Kinetics of the Oxidation of Methyl Phenyl Sulfide by Hydrogen Peroxide in the Presence of Hydrocarbonate Anion

The oxidation of methyl phenyl sulfide in water and water-alcohol mixtures takes place both by a noncatalytic mechanism and with the participation of hydrogen peroxide as catalyst; in the presence of ammonium hydrocarbonate it takes place by a mechanism involving HCO ₄ ⁻ as a more active oxidant than hydrogen peroxide (>100 times). In water-alcohol media (ethylene glycol, isopropyl alcohol, tert-butanol) the rate decreases in the order H₂O > EG > IPA > TBA. The reactivity of organic sulfides varies in the following way: MeSPh ≈ EtSPh << Et₂S. The results were interpreted from the standpoint of a molecular mechanism of oxidation of the sulfide with H₂O₂ and HCO ₄ ⁻ through a polar transition state, containing the HOX molecule (X = H, OH, OR) as acid-base catalyst.__________Translated from Teoreticheskaya i Eksperimental’naya Khimiya, Vol. 41, No. 2, pp. 94–99, March–April, 2005.     

Forced oscillations of a gas bubble in a spherical volume of a compressible liquid

A spherically symmetric problem of oscillations of a single gas bubble at the center of a spherical flask filled with a compressible liquid under the action of pressure oscillations on the flask wall is considered. A system of differential-difference equations is obtained that extends the Rayleigh-Plesset equation to the case of a compressible liquid and takes into account the pressure-wave reflection from the bubble and the flask wall. A linear analysis of solutions of this system of equations is performed for the case of harmonic oscillations of the bubble. Nonlinear resonance oscillations and nearly resonance nonharmonic oscillations of the bubble caused by harmonic pressure oscillations on the flask wall are analyzed. Ufa Scientific Center, Russian Academy of Sciences, Ufa 450000. Translated from Prikladnaya Mekhanika i Tekhnicheskaya Fizika, Vol. 40, No. 2, pp. 111–118, March–April, 1999.     

Reaction of Amino Acid Salts with 4-Nitrophenyl Acetate under Solid-Liquid Phase Transfer Conditions

The reaction of amino acid salts with 4-nitrophenyl acetate in a system consisting of a solid phase and organic solvent with catalysis by crown ethers and quaternary onium salts may be carried out both on the phase separation surface and in the organic phase depending on the nature of the participants in the phase transfer catalysis reaction.     

Simple antitumor model compounds for cross-conjugated cyclopentenone prostaglandins

1. Download : Download high-res image (44KB)
2. Download : Download full-size image

     

Nucleophilic oxidizing systems based on hydrogen peroxide for decomposition of ecotoxicants

The kinetics of oxidation of methylsulfanylbenzene and nucleophilic decomposition of diethyl 4-nitrophenyl phosphate with hydrogen peroxide in the presence of ammonium hydrogen carbonate or boric acid in aqueous, aqueous-alcoholic, micellar, and microemulsion media were studied. Quantitative parameters of the examined processes were determined, and the possibility of using hydrogen peroxide for the design of oxidative nucleophilic decontaminating systems was demonstrated.     

New atropoisomeric alkenylphenylglycine derivatives: Synthesis of (5R*)- and (5S*)-isomers of (1R*,3aR*,4S*,11S*)-3a,5,9,11-tetramethyl-4,5-dihydro-3aH-1,4-methano[1,3]oxazolo[3,2-a]quinolin-2-one

We synthesized methyl ester of N-(1-methylbut-2-en-1-yl)-N-phenylglycine which underwent acid catalyzed aromatic amino Claisen rearrangement to provide methyl-N-[2-(1-methylbut-2-en-1-yl)phenyl]glycinate. A mixture of syn- and anti-atropisomeric methyl-N-acetyl-N-[4-methyl-2-(1-methylbut-2-en-1-yl)phenyl]glycinates was obtained either by the reaction of this ester with acetyl bromide or by the reaction of the sodium salt of N-acetyl-2-(1-methylbut-2-en-1-yl)-4-methylaniline with methyl bromoacetate. Upon saponification of the synthesized ester mixture the syn-atropisomer of N-acetyl-N-[4-methyl-2-(1-methylbut-2-en-1-yl)phenyl]glycine was isolated by fractional crystallization. Treatment of the obtained acids with acetic anhydride, ethyl chloroformate, dicyclohexylcarbodiimide or isopropenylacetate leads to compounds of 4,5-dihydro-3aH-methano[1,3]oxazolo[3,2-a]quinolin-2-one structure.     

Synergism and antagonism in phase transfer catalysis

Synergism and antagonism phenomena in phase transfer catalytic reactions have been considered. The factors responsible for the Synergism in the catalysis by an onium salt-crown ether mixture have been determined. Special attention have been paid to quantitative estimation of synergism and antagonism. The influence of addition of water on the rates of the reactions in solid-liquid systems have been discussed.In memory of the 75th anniversary of Member of the Academy of Sciences of Ukrainian SSR L. M. Litvinenko.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2108–2114, November, 1995.     

Selberg’s one-dimensional sieve with Buchstab weights of new type

In this paper we study Selberg's sieve method with Buchstab weights of new type. The theorem proved in this paper gives a more advantageous choice of the parameters of a one-dimensional weighted sieve as compared to previous results. Translated fromMatematicheskie Zametki, Vol. 66, No. 1, pp. 38–49, July, 1999.     

Effect of an external magnetic field on the orientational phase diagrams of (011) crystalline garnet ferrite plates with combined anisotropy

The effect of an external magnetic field on uniform magnetic states in (011) crystalline garnet ferrite plates with combined anisotropy is theoretically studied. Under the action of the field, the magnetic symmetry of the crystals is reduced and the pattern of spin-reorientation phase transitions, which depends significantly on the magnetic field strength and direction, changes. Curves of critical fields are found, and the general law of magnetization reversal in the (011) plates due to rotation is derived.