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Zaikov G. E. Bichutinskii A. A. Maizus A. K. Émanuél' N. M. 《Russian Chemical Bulletin》1968,17(8):1649-1653
Russian Chemical Bulletin - 相似文献
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The gas-phase reaction of ozone with a series of unsaturated oxygenates and with 1-pentene has been studied at ambient T (287–296 K) and p=1 atm. of air. Reaction rate constants, in units of 10−18 cm3 molecule−1 s−1, are 0.22±0.05 for 2 (5H)-furanone, 1.08±0.20 for methacrolein, 1.74±0.20 for crotonaldehyde, 5.84±0.39 for methylvinyl ketone, 1.05±0.15 for methyl acrylate, 3.20±0.47 for vinyl acetate, 59.0±8.7 for cis-3-hexenyl acetate, 154±30 for ethylvinyl ether, ≥(315±23) for linalool, and 10.9±1.4 for 1-pentene. The results are compared to literature data for the compounds studied and for other unsaturated oxygenates, and are discussed in terms of reactivity toward ozone as a function of the nature, number, and position of the oxygen-containing substituents (SINGLEBOND)CHO, (SINGLEBOND)C(O)R, (SINGLEBOND)C(O)OR, and (SINGLEBOND)OC(O)R. Atmospheric implications are briefly examined. © 1998 John Wiley & Sons, Inc. Int. J Chem Kinet: 30: 21–29, 1998. 相似文献
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N. N. Novitskaya R. V. Kunakova G. A. Tolstikov 《Chemistry of Heterocyclic Compounds》1976,12(4):398-401
The oxidation of thiabicyclotridecenes with various oxidizing agents proceeds selectively and, depending on the amount and strength of the oxidizing agent, gives sulfoxides, epoxy sulfoxides, or epoxy sulfones. The sulfur atom is initially oxidized, after which the double bond either undergoes epoxidation or hydroxylation.See [9] for communication XIITranslated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 475–478, April, 1976. 相似文献
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Peerannawar Swarada Sood Abha Brown Alicia Schäfer Christian Alonzo Judith Sutton Steven Christianson Matthew Stocking Raven Naclerio Nicole Török Béla Landge Shainaz M. 《Structural chemistry》2019,30(5):1941-1956
Structural Chemistry - The effect of solvents has been found as a crucial factor in determining the regioselectivity of the hydroxyalkylation of indole with trifluoroacetaldehyde hemiacetals. The... 相似文献
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The absolute rate constant for the reaction of methyl radicals with ozone has been measured as a function of temperature. Small concentrations of CH3 were generated by flash photolyzing CH3NO2 at 193 nm with an ArF laser. A photoionization mass spectrometer was used to follow the rate of decay of CH3 at various ozone concentrations. The resulting rate constants could be fit by the expressions over the temperature range of 243–384 K. These rate constants can be modeled by simple transition state theory using reasonable parameters for the activated complex. Use of this rate constant shows that less than 1% of the methyl radicals formed in the stratosphere react with ozone. 相似文献
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A number of indenes have been prepared in good yields by treating o-bromobenzyl zinc bromide 1 with various terminal and internal alkynes in the presence of a nickel catalyst. The nickel-catalyzed carboannulation reaction was successfully extended to the synthesis of indane derivatives by reaction of 1 with acrylates and styrene. 相似文献
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V. E. Bel'skii 《Russian Chemical Bulletin》1998,47(2):265-268
Regression analysis of the solvent effects on the rate constants of nucleophilic substitution at the phosphoryl group was
performed with the use of the empirical parameters of solvent polarity which characterize the ability of the solvents to electrophilic
and nucleophilic solvation. The nucleophilic solvation of reagents by solvents, as a rule, favors the phosphorylation reactions.
In the phosphorylation reactions of anionic nucleophiles, the electrophilic solvation of anions influences negatively the
reactions rates. The phosphorylation of amines by chlorides of phosphorus acids is facilitated by the electrophilic solvation
of a separated anion.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 271–274, February, 1998. 相似文献
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Summary The gas chromatographic reactor technique was used to study the kinetics of dicyclopentadiene dissociation in several liquid phases (Versamid 900, neopentyl glycol sebacate, Triton X-305, Carbowax 6000, ethylene glycol phthalate and diethylene glycol succinate). Reaction rates and Arrhenius parameters are reported in the temperature range of 170–200°C. Kinetic data for the lower polarity liquid phases are in good agreement with literature values for liquid phases of the same nature reported previously. Reaction rates are higher when polar liquid phases are used. This behavior can be explained as a result of side reactions which lead to high molecular weight compounds which can be observed in the reaction chromatogram. 相似文献
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Bile salts form supramolecular aggregates with two binding sites with different properties. The guest binding dynamics to the aggregates and guest protection from species in the aqueous phase were investigated using fluorescence and laser flash photolysis experiments. Sodium cholate, deoxycholate and taurodeoxycholate were used as bile salts and acetonitrile or ethylene glycol were added as co-solvents to water in order to alter the binding properties of 1-ethylnaphthalene and 1-naphthyl-1-ethanol with the aggregates. The binding dynamics are faster and protection efficiencies are lower for guests bound to cholate and in the presence of either co-solvent. 相似文献
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G. G. Midyana R. G. Makitra E. Ya. Pal’chikova 《Russian Journal of Organic Chemistry》2014,50(2):165-167
Generalization of data on the reaction rate of catalyzed process between mercaptans and phenyl isocyanate in various media led to the conclusion that the reaction rate increased due to the specific, especially nucleophilic, solvation. The primary reaction stage is the formation of a complex between the acidic mercaptan and a base, a catalyst (triethylamine) or basic solvent. 相似文献
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A combined computational and experimental kinetic study on the Henry reaction is reported. The effects of solvation on the transition structures and the rates of reaction between nitromethane and formaldehyde, and between nitropropane and benzaldehyde are elucidated with QM/MM calculations. 相似文献
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Alkylidene carbenes, when generated from o-aminobenzophenones and lithiated trimethylsilyldiazomethane, give a mixture of alkyne (by rearrangement) and indole (by N-H insertion). It has been found that this ratio of indole to acetylene shows a linear dependence on the polarity of the ethereal solvent. 相似文献
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Effect of para-substituents and solvent polarity on the formation of triphenylboroxine.amine adducts
Density functional theory (B3LYP//6-311+G) calculations including Poisson-Boltzmann implicit solvent and NMR were used to study the formation of a series of para-substituted triphenylboroxine.amine adducts with respect to their phenylboronic acid monomers and free amine in solution. Our calculations suggest that the intermediate prior to forming trimer.amine is a dimer.amine adduct. Formation of dimer.amine can proceed via two pathways. Electron-donating substituents favor dimerization of two monomers before addition of the amine, and electron-withdrawing substituents favor formation of a monomer.amine adduct before addition of the second monomer. We also find that pi-electron acceptors destabilize formation of the dimer and trimer with respect to its monomers. Electron-withdrawing substituents favor adduct formation. Adduct formation is enthalpically stabilized by increasing the polarity of the solvent but differential solubility of the monomer compared to trimer.amine also has an effect on the equilibrium constant. 相似文献