Role of the medium in the cooxidation of cumene with benzyl alcohol

The kinetic parameters of the cooxidation of cumene with benzyl alcohol were measured in various solvents. The main influence of the medium on the reaction is determined by the polarity and nucleophilicity of the solvents. With increase in the per-volume fraction of the alcohol in the cooxidized mixture, the sensitivity of the process to the composition of the solution increases. The dependence of the kinetic cooxidation parameters on the empirical parameters of the solvents was analyzed, and it was shown that the medium substantially influences the activity of the peroxy radicals of the alcohol. The activity of the cumylperoxy radicals does not change appreciably.Translated from Teoreticheskaya i Éksperimental/naya Khimiya, Vol. 26, No. 5, pp. 606–610, September–October, 1990.     

Spectroscopic determination of photostimulated reactions in halomethane solutions of phthalimide and its derivatives

The photochemical reactions of phthalimide, N-benzylphthalimide, 3-and 4-aminophthalimide in the presence of halomethanes have been studied. The end products of the reaction were identified. It was found that phthalimides do not undergo a chemical reaction under the action of light, and their transformations are determined by a reaction with the active products of the photodissociation of tetrachloromethane in the presence of oxygen.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 23, No. 4, pp. 480–484, July–August 1987.     

Kinetics of the initial stage of catalytic radical chain oxidation of cumene with catalyst deactivation

We have developed a method for estimating the rate constant for the reaction of catalyst deactivation in a radical chain process in the presence of catalysts with low stability. Its applicability is demonstrated in the reaction of oxidation of cumene in the presence of alkylammonium halides.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 30, No. 2, pp. 69–74, March–April, 1994.     

Friedel-Crafts alkylation of indoles

The alkylation of indole and 2-methylindole with alkyl halides in the presence of a complex catalyst — dipyridinezinc chloride — was investigated. Nitromethane was used as the solvent. 3-Alkylindoles were obtained in 30–80% yields in all cases. The reaction mechanism is discussed. Data from the PMR and mass spectra are presented.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 921–924, July, 1978.     

Reduction of nitrobenzene to aniline with carbon monoxide and water

Modified catalyst systems composed of palladium or its chloride and co-catalysts such as FeCl₃, Fe₂O₃, metallic Fe-powder, metallic Fe-wire net, iodine, pyridine or aniline, applied in the reduction of nitrobenzene to aniline in the presence of carbon monoxide and water are described. The reaction proceeds at 150–180 °C and 2.5–7 MPa gauge pressure. After 1–7 h the reaction was complete, reaching nitrobenzene conversions of 98–100%. Selectivity of the reaction with respect to aniline was also 100%.     

Catalytic Self-Hydrogenation of Anthracene in the Presence of a Magnesium–Anthracene Adduct

The catalytic properties of cluster magnesium derivatives were studied using the self-hydrogenation reaction of unsaturated compounds as an example. In the presence of a cluster magnesium–anthracene adduct at 150–298 K, the self-hydrogenation of anthracene occurred with yields of up to 40 molecules per atom of magnesium.     

Addition of thiols to (-)-carvone

Polyfunctional thioterpenoids were formed in the presence of a Lewis-acid catalyst by reaction of (-)-carvone with thiols that involved the endocyclic double bond and the carbonyl.Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 393–395, September–October, 2004.     

Reductive alkylation of p-phenylenediamine and its hydroquinone complex with ketones in presence of rhenium and palladium sulfides

Conclusions Conditions were found (150–200°, hydrogen pressure 110–150 atm, reaction time 3 h) for the reductive alkylation of p-phenylenediamine and its hydroquinone complex with acetone, butanone, and cyclohexanone in presence of Re₂S₇ or PdS as catalyst, and N,N'-diisopropyl-, N,N'-di-s-butyl-, and N,N'-dicyclohexyl-p-phenylenediamines and their hydroquinone complexes were obtained in 60–90% yield.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1601–1605, July, 1968.     

Reaction of the Intermetallic Compound SmFe11Ti with Gaseous Ammonia

The reaction of the intermetallic compound SmFe₁₁Ti with ammonia at the initial NH₃ pressure of 0.6 – 0.8 MPa in the temperature range 150 – 450 °C in the presence of 10 wt % NH₄Cl as activator was studied. Depending on the reaction temperature, SmFe₁₁Ti undergoes both hydrogenation to form a hydride phase of the starting intermetallic compound and disproportionation to form a hydride phase of a new intermetallic compound. The reaction products are finely dispersed powders. The magnetic properties of the products were studied.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005, pp. 881–885.Original Russian Text Copyright © 2005 by Fokin, Shul’ga, Tarasov, Fokina, Korobov, Burlakova, Shilkin.     

Synthesis and Properties of First Bis(fluoreno)crownophanes

Alkylation of 2,7-dihydroxy-9H-fluoren-9-one with 2-(2-chloroethoxy)ethanol, 2-[2-(2-chloroethoxy)-ethoxy]ethanol, and 2-{2-[2-(2-chloroethoxy)ethoxy]ethoxy}ethanol in dimethylformamide in the presence of potassium carbonate gave 78–80% of the corresponding diols which were treated with p-toluenesulfonyl chloride in a dioxanechloroform mixture in the presence of triethylamine at 0– 5°C (30 h). The resulting bis(p-toluene-sulfonates) were brought into condensation with 2,7-dihydroxy-9H-fluoren-9-one in a very dilute solution in dimethylformamide containing anhydrous potassium carbonate at 80–85°C. Appropriate treatment of the reaction mixture, followed by chromatographic purification afforded 53–27% of the first representatives of a new class of cyclophanes, bis(oxofluoreno)crownophanes. Raising the temperature to 95–105°C resulted in an appreciable decrease of the product yield. The yield of the target products did not increase on replacement of potassium carbonate by cesium carbonate.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1, 2005, pp. 144–149.Original Russian Text Copyright © 2005 by Lyapunov, Kirichenko, Kulygina, Luk’yanenko.     

Kinetics and Stoichiometry of the Reaction of Ozone with Fullerene C60 in a CCl4 Solution

The stoichiometry (1 : 1) and the numerical value of the rate constant of the reaction of a fullerene with ozone (1.2 × 10³ l mol^–1 s^–1) at 0°C were determined. A kinetic study of the reaction revealed the presence of an active impurity in high-purity samples. Suggestions as to the structure of this impurity were proposed based on the rate constant of its reaction with ozone. In contrast to simple aromatic compounds, the reaction of the fullerene with the first molecule of ozone dramatically (by several orders of magnitude) decreased the reactivity of the other C=C bonds in the molecule.     

Spectrophotometric determination and kinetic studies of condensation of aromatic aldehydes with 1,3-dimethylbarbituric acid

The condensation reaction of 1,3-dimethylbarbituric acid with aromatic aldehydes in ethanol has been investigated spectrophotometrically at 25–35°C. The reaction follows overall second-order kinetics, first-order each in reactant. From the dependence of the rate constants on temperature, activation parameters have been calculated. The rate of condensation increases with the presence of electron donating groups on the aromatic ring of the aldehyde. The rate-determining step involves dehydration of the aldol intermediate. The reaction was found to be catalyzed by HCl solutions. Based on this reaction, determination of 10 aromatic aldehydes in a concentration range of 0.13–70.25 μg/ml is proposed. The method was applied for determination of barbituric and 1,3-dimethylbarbituric acids also.     

Measurement and Modeling of Th Sorption onto TiO(2)

The sorption and desorption of Th onto TiO₂ (10 g/L) was studied as a function of pH (1–11), ionic strength (0.005–0.1 M NaCl, NaClO₄), thorium concentration (from 1 × 10⁻⁹ to 3 × 10⁻² M), and carbonate concentration (up to 10⁻² M) using ²³⁴Th tracer. The results indicate the reversible formation of an inner sphere complex with a strong pH dependence. No effect of the carbonate on sorption could be measured in the pH range investigated (5–10.5). The data were fitted with five different conceptual models (constant capacitance, diffuse layer, Stern, triple layer, and a nonelectrostatic model) using FITEQL. Different hydroxy complex surface reactions were tried, one at a time, varying the site density (1–12 sites/nm²). The reaction that provided the best fit depended strongly on the surface site density and the model used. To be able to fit a reaction to the pH-dependent data with the compact layer models, the effect of the electrostatic term had to be decreased by decreasing the site density below 5 sites/nm². None of the electrostatic models could be used to fit all of the isotherm data. The nonelectrostatic model could be used to reasonably fit both the pH-dependent and isotherm data.     

Reaction of dialkyl(or aryl) dichlorosilanes with alkali metals in presence of conjugated dienes

Summary The reaction of dialkyl(or aryl)dichlorosilanes with conjugated dienes in presence of alkali metals in a tetrahydrofuran medium leads to the formation of unsaturated sila-hydrocarbon polymers with silicon atoms in the main chain and molecular weights of 1000 or over, and also the corresponding silacyclopentenes (yields 0–10%) and divinylsilacyclopentanes (yields 10–50%). The relative amounts (yields) of these products depend both on the nature of the reactants and on the reaction conditions.Translated from Izvestiya Akademii Nauk SSR, Seriya Khimicheskaya, No. 5, pp. 840–844, May, 1964     

Co-catalysis by transition metal ions in the hydrogen ion catalysed oxidation of iodide ions. A kinetic study

The reaction between KI and [Fe(CN)₆]^3– ion, catalysed by hydrogen ions, was found to be catalysed further by PdCl₂. Separate reactions under similar conditions, studied in the absence as well as in the presence of PdCl₂ catalyst, were found to follow first order kinetics w.r. to [Fe(CN)₆]^3– and [H⁺], while the order was two w.r. to [I^–]. [Fe(CN)₆]^4– ions were found to have a negative effect while changes in ionic strength of the medium do not effect the reaction velocity. Reaction in the presence of PdCl₂ showed direct proportionality w.r. to [PdCl₂]. The rate and extent of the reaction, which takes place even at zero [PdCl₂] in the co-catalysed reaction, was calculated and was found to be in accordance with the rate values of the separately studied reaction at similar concentrations without adding PdCl₂.     

Synthesis of 2-(acylmethyl) benzo-1,3-oxathiols from acetylenic ketones

2-(Acylmethyl)benzo-1,3-oxathiols were synthesized by reaction of acetylenic ketones with o-mercaptophenol in alcohol in the presence of a catalyst — triethylamine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1328–1329, October, 1975.     

Cu-superconductors in organic catalysis, II. The conversion of benzyl alcohol on various Cu-catalysts

The catalytic conversion of benzyl alcohol to toluene and benzaldehyde was performed on YBa₂Cu₃O_7–x (Y–Ba–Cu–O) in the presence of hydrogen at 250–400°C. The catalytic characteristics of Y–Ba–Cu–O were compared with those of CuO, Cu/SiO₂ and Y₂BaCuO₅. The structural changes in the catalysts during the reaction were measured by means of XRD and SEM. It was found that the oxidation state of the copper in Y–Ba–Cu–O was a considerable factor in the conversion of benzyl alcohol.Part I:React. Kinet. Catal. Lett. 51, 61 (1993).     

Catalytic coprocessing of waste plastics and petroleum residue into liquid fuel oils

Waste plastics of different types were catalytically coprocessed with petroleum residue of light Arabian crude oil in the presence of a number of catalysts. The purpose of the study was to explore effects of various conditions such as catalyst type, amount of catalyst, reaction time, pressure and temperature on the product distribution. The waste plastic studied included low-density polyethylene (LDPE), high-density polyethylene (HDPE), polystyrene (PS) and polypropylene (PP). A series of single (waster plastic with catalyst) and binary (waste plastic and residue with catalyst) reactions were carried out in an autoclave reactor under variable reaction conditions. The reaction conditions used were 1, 3 and 5 wt.% catalysts, 30–120 min reaction time, 400–430 °C reaction temperature and 500–1200 psi hydrogen pressure. The product distribution achieved for residue/plastic/catalyst system showed higher yields of liquid fuels as compared to residue/plastic system. Hydrocarbon gases were formed as well along with heavy oils, insoluble gums and coke. At the reaction conditions of 3 wt.% NiMo catalyst, 90 min reaction time, 1200 psi hydrogen gas pressure, 430 °C temperature and residue to plastic feed ratio of 3:2 (wt.) afforded maximum conversion of the plastics into liquid fuel oils.     

Reaction of Graphite with Sulfuric Acid in the Presence of KMnO<Subscript>4</Subscript>

The reaction of graphite with sulfuric acid in the presence of KMnO₄ (oxidant : graphite ratio 0.027–0.55) involves consecutive and concurrent reactions: graphite intercalation and direct oxidation of the carbon matrix. The properties of graphite bisulfate and its reaction products are determined by the stage number of the intercalation compound; the decomposition enthalpies of the stage I–IV graphite bisulfate correlate with the enthalpies of graphite intercalation with sulfuric acid.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 2, 2005, pp. 184–191.Original Russian Text Copyright © 2005 by Sorokina, Khaskov, Avdeev, Nikol’skaya.     

Hydrosilylation and hydrogermylation of 3-OXO-1,2-Benzisothiazoline-2-(2-propynyl)-1,1-dioxide

The addition of triethylsilane and triethylgermane to N-propargylsaccharin in the presence of the Speier catalyst gives the gem adduct with trans configuration. This pathway accounts for 75–80% of the reaction.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2889–2891, December, 1991.