Reaction of toluene with ozone in the liquid phase

Reaction of toluene with ozone in acetic anhydride was studied. The dependence of the direction, selectivity, and extent of oxidation on the reaction temperature, solvent nature, and catalyst composition was examined.     

Kinetics and mechanism of 4-acetoxytoluene oxidation by ozone in an acetic anhydride solution in the presence of manganese bromide catalysts

The kinetics of the reaction of ozone with 4-acetoxytoluene in an acetic anhydride solution in the presence of a manganese bromide catalyst is reported. Under these conditions, the major reaction products are 4-acetoxybenzylidenediacetate (68.0%), 4-acetoxybenzyl acetate (18.5%), and 4-acetoxybenzyl bromide (1.6%). The effect of manganese(II) acetate and potassium bromide on the selectivity of oxidation at the methyl group has been investigated. A probable redox catalysis mechanism explaining the experimental data is considered.     

Kinetics and mechanism of the liquid-phase reaction of 2,4-dinitrotoluene with ozone in the presence of manganese(II) acetate

The kinetics and the mechanism of the liquid-phase oxidation of 2,4-dinitrotoluene with ozone in the presence of manganese(II) acetate have been investigated. The major products of 2,4-dinitrotoluene oxidation with ozone in acetic anhydride are 2,4-dinitrobenzyl acetate (65.8%) and 2,4-dinitrobenzylidene diacetate (18.8%). The effect of the manganese(II) acetate concentration on the selectivity of substrate oxidation at the methyl group is reported. A redox catalysis mechanism providing an explanation to experimental data is considered.     

The reaction of ozone with thiophene in the gas phase

The reaction between ozone and thiophene was studied from 30 to 125°C over a pressure range of 0.005-0.3 torr ozone and 0.1-1 torr thiophene. The most abundant product was O₂ with smaller amounts of CO₂ and SO₂. The mass balance was 100% for oxygen and approached 100% for sulfur at the higher values of [O₃]₀. The carbon balance, however, was only 25% and no H-containing products were found, suggesting that the missing product is a hydrocarbon which may be a polymer. The rate law found was -d[O₃]/dt = k₁[Th] [O₃] + k₂ [Th] [O₃]² where log k₁(M^?1 · sec^?1) = 7.8 ± 0.5 - (8400 ± 700)/2.3RT, and log k₂(M^?2 · sec^?1) = 12.4 ± 0.4 - (4700 ± 400)/2.3RT. Added O₂ had no effect on k₁ but reduced k₂ to a limiting value. It is thus not possible to measure the primary rate constant in this system by measuring the overall rate in the presence of oxygen, and this restriction may also apply to other ozone systems. A mechanism is postulated involving two chain sequences, one of which is inhibited by added O₂. A comparison with other ozone systems is made, and the chain lengths are far greater for ozone + thiophene than other systems, under the conditions employed. Possible intermediates in the mechanism are discussed.     

Reaction of ozone with five-membered hetarenes in a liquid phase

Oxidation of pyrrole, furan, and thiophene by ozone in a solution of glacial acetic acid was studied. Peroxide compounds, which are, presumably, dimers of linear structure, were found as primary products. The kinetics of ozonolytic reactions with five-membered hetarenes was examined, and rate constants and experimental stoichiometric coefficients for ozone were determined.     

Liquid-phase reactions of isomeric methylphenols with ozone

Ozonation of isomeric methylphenols in acetic anhydride was studied. Here, acetic anhydride acts simultaneously as solvent and acylating agent. In the presence of a mineral acid methylphenols were converted into methylphenyl acetates during preparation of solutions for ozonation. The major products in the oxidation of isomeric methylphenyl acetates with ozone were aliphatic peroxides (80–90%); oxidation of the methyl group gave rise to the corresponding acetoxybenzyl acetates (7–14%) and acetoxybenzylidene diacetates (3–6%). A probable scheme for the liquid-phase oxidation of methylphenyl acetates with ozone in acetic anhydride was proposed.     

Direct experimental evidence for a heterogeneous reaction of ozone with bromide at the air-aqueous interface

Recent experimental and theoretical evidence has indicated an enhancement of the heavier halide ions at the air-aqueous interface, relative to their bulk concentrations. This, along with an order of magnitude discrepancy between measured and predicted Br2 production in the reaction of ozone with deliquesced NaBr aerosol, has led to the suggestion that an interface reaction occurs between ozone and bromide. We have used harmine, a beta-carboline alkaloid, as an interface-sensitive fluorescent pH probe in order to measure pH changes associated with the interfacial reaction of ozone and bromide. The rate of pH change depends upon the bulk bromide concentration in a way which is well described by a Langmuir-Hinshelwood kinetic model. In the presence of octanol at the interface, the rate of pH change tracks the octanol adsorption isotherm, as expected if octanol enhances the concentration of ozone at the surface.     

The kinetics of the reaction between manganese pentacarbonyl bromide and β-alanine

Manganese pentacarbonyl bromide reacts with β-alanine to give manganese tricarbonyl bis-(β-alanine) bromide. The kinetics of this reaction are described, the first step under thermal and the second under photochemical conditions. Rate constants in 50% aqueous methanol and in 50% aqueous dimethyl sulphoxide, and the activation enthalpy, entropy, and volume for the first step in 50% aqueous methanol are reported. The kinetics results suggest dissociative mechanisms for both stages, though there are some unusual features of the first step. Some rate constants for the reactions of manganese pentacarbonyl bromide with glycine and of rhenium pentacarbonyl bromide with β-alanine are also given.     

Spectrophotometric study of the reaction of titanium with bromopyrogallol red in the presence of cetylpyridinium bromide

Optimal conditions were found for the reaction of Ti(IV) with bromopyrogallol red (λ = 625 nm, pH = 2.5, c_DG = 4 × 10^?5M, c_CPB = 5 × 10^?4M) and a new method was developed for the spectrophotometric determination of titanium in the concentration range 0.05–0.5 μg ml^?1. A mechanism was proposed for the studied reaction on the basis of a kinetic study.     

Methanol dehydrogenation in the liquid phase with Ru/active carbon catalyst

In contrast to the gas-phase reaction, the liquid-phase reaction of methanol with Ru/C catalyst scarcely gave methane. Product distribution strongly depended on reaction conditions even under atmospheric pressure.     

The overall reaction process of ozone with methacrolein and isoprene in the condensed phase

The reaction of isoprene and methacrolein with ozone was investigated at different stages in the condensed phase at temperatures from 15 to 265 K by IR spectroscopy. The results revealed the following overall reaction process: the generation of primary ozonide (POZ), then its decomposition, and finally conversion into secondary ozonide (SOZ), which supported the Criegee mechanism. In the POZ and SOZ of isoprene, ozone cyclo-added preferentially to the double-bond that is not substituted by the methyl group. For methacrolein, the mainly detected SOZ is claimed to be MACSII formed by recombination of the intermediate CH(2)OO radical with aldehyde carbonyl of methylglyoxal in stead of the ketone carbonyl group. Theoretical calculations were performed at the B3LYP//MP2/6-311++G (2d, 2p) level to analyze the resulting spectrum. The good agreement between the calculated infrared spectra of POZ and SOZ and the experimental spectra supports the above-described findings.     

A spectrophotometric study of the reaction of tin with bromopyrogallol red in the presence of cetylpyridinium bromide

A sensitive spectrophotometric method for determining tin in the range 0.04–0.8 μg ml^-1 has been developed on the basis of a detailed study of the colour reaction of tin with bromopyrogallol red in the presence of cetylpyridinium bromide. The method proved satisfactory for various industrial and natural samples. The kinetics of the reaction and the mechanism of the influence of cetylpyridinium bromide are discussed.     

Kinetics and mechanism of the reaction of benzyl bromide with copper in dimethylacetamide in the presence of oxygen

The reaction of copper metal with benzyl bromide in dimethylacetamide in the presence of oxygen has been studied. Oxidative dissolution of copper follows the single-electron transfer mechanism with formation of benzaldehyde, benzyl alcohols, and copper(II) coordination compounds. The kinetic and thermodynamic parameters of the process have been determined by resistometry. Intermediately formed species have been identified and quantitated, and the reaction stereochemistry has been studied. The reaction mechanism is discussed.     

Dynamic solid phase microextraction sampling for reactive terpenes in the presence of ozone

Dynamic gas sampling using solid phase microextraction (SPME) was evaluated for recovery of reactive terpenes and terpenoids in the presence of ozone. For limonene, α-terpineol and dihydromyrcenol in the 20-60 ppb range, this method achieves >80% recovery for ozone mixing ratios up to 100 ppb. Both the experimental results and a model analysis indicate that higher ozone concentrations and longer sampling times result in lower percent recovery. Typically greater than 90% recovery and ppb level method detection limits were achieved with a 5 min sample time. Increasing the flow rate from 100 to 400 sccm flow (5-20 cm s⁻¹) through the active sampler did not significantly affect sensitivity or recovery in most cases, probably due to negligible mass-transfer improvements. The recovery for each compound improves when sampling from a mixture of different species than that from a single compound sample. This may be due to competition for ozone amongst adsorbed species. Dynamic SPME sampling can improve detection and quantification of terpenes in reactive environments, especially for low vapor pressure (<5 mm Hg at 25 °C) compounds that can be adsorbed to ozone scrubbers used in other methods.     

离子液体催化合成乙二醇丁醚醋酸酯

以乙二醇单丁醚和冰醋酸为原料,在离子液体N-甲基吡咯烷酮硫酸氢盐([Hnmp] HSO4)催化下,合成了乙二醇丁醚醋酸酯.考察了催化剂用量、物料配比、反应时间、带水剂等因素对反应收率的影响.利用气相色谱仪分析了产物的纯度;利用核磁共振谱仪和质谱仪表征了产物的结构.结果表明,合成产物的纯度大于99.0％.[Hnmp]H ...     

Synthesis of cyclic disulfides using didecyldimethylammonium bromide as phase transfer catalyst

A convenient, practical and general method for the synthesis of symmetrical and unsymmetrical cyclic disulfides based on the reaction of sulfur with sodium sulfide in the presence of didecyldimethylammonium bromide (DDAB) as a phase transfer catalyst is described.     

The reaction of cyclones with isomeric dihydronaphthalenes

Summary In the reaction of cyclones with isomeric dihydronaphthalenes there is reduction of the cyclones to dihydro-cyclones because of dehydrogenation of the dihydronaphthalenes.     

低浓度煤层气在发烟硫酸中液相部分氧化的催化剂研究

在发烟硫酸溶液中,对低浓度煤层气液相部分氧化的催化剂进行了筛选,考察了硫酸盐化合物系列、过渡金属化合物系列、碘化合物系列对低浓度煤层气液相部分氧化的催化活性,对筛选出的碘催化剂进行了催化剂加入量的考察,并对碘催化剂的催化机理进行了讨论。结果表明,碘单质的催化效果最好,低浓度煤层气中甲烷转化率可达79.69%,甲烷选择性可达83.74%。在对碘催化剂加入量的考察中发现,随着碘催化剂加入量的增加,低浓度煤层气的转化率先增加,达到最大值以后,再逐渐减小。根据甲烷在发烟硫酸溶液中液相部分氧化的反应机理,提出低浓度煤层气在发烟硫酸溶液中液相部分氧化的反应机理属于亲电反应机理。     

Epoxidation of cycloolefins with hydrogen peroxide in the presence of heteropoly acids combined with phase transfer catalyst

Oxidation of cycloolefins (cyclohexene, cyclooctene, and cyclododecene) with a 30% solution of hydrogen peroxide at 65 °C in the presence of heteropoly acids (HPA) H₃PW_12–x Mo _x O₄₀ (x = 0—12), which are precursors of active peroxo complexes, and phase transfer catalysts Q⁺Cl^–, where Q⁺ is the quaternary ammonium cation containing C₄—C₁₈ alkyl groups or [C₅H₅NC₁₆H₃₃]⁺, was studied. The catalytic activity decreases in the HPA series: H₃PW₁₂O₄₀ > H₃PW₉Mo₃O₄₀ > H₃PW₆Mo₆O₄₀ > H₃PW₃Mo₉O₄₀ > H₃PMo₁₂O₄₀. The state of the H₃PW₁₂O₄₀—I₂I₂ system was studied using UV, IR, and ³¹P NMR spectroscopies with variation of the [H₂O₂] : [HPA] ratio from 2 to 200 during cyclohexene epoxidation. Despite different catalytic precursors, the reaction proceeds through the same peroxo complex.