Kinetics and mechanism of oxidation of aniline and substituted anilines by isoquinolinium bromochromate in aqueous acetic acid

Oxidation of anilines by isoquinolinium bromochromate (IQBC) in aqueous acetic acid leads to the formation of corresponding azobenzenes. The reaction is first order with respect to both aniline and IQBC and is catalyzed by hydrogen ion. The rate of oxidation decreases with increasing dielectric constant of solvent, indicating the presence of an ion-dipole interaction. The rate of oxidation decreases with increase in concentration of KCl, possibly due to the formation of less reactive species by interaction of Cl^- and protonated IQBC. The specific rate of oxidizing species anilines reaction correlates with substituents constant affording a negative reaction constant. Hammett plot is found to be valid and the correlation between enthalpies and free energies of activation is reasonably linear with an isokinetic temperature of 401 K.     

Coulometric generation of acetylions by oxidation of mercury in acetic anhydride and in acetic acid/acetic anhydride mixture

Coulometric generation of acetyl (CH₃CO⁺) ions by oxidation of mercury in acetic anhydride and in acetic acid/acetic anhydride (5:95, v/v) is described. Current/potential curves for solvents, titrated bases, indicator and mercury showed that in both these solvents mercury is oxidized at potentials which are much more negative than those for the titrated bases and other components present in the solution. Quinoline, triethanolamine, triethylamine, pyridine and quinolin-8-ol in acetic anhydride, as well as triethylamine, 2,2′-bipyridine, 2,4,6-collidine, pyridine and sodium acetate in acetic acid/acetic anhydride were titrated with acetyl ions generated by the oxidation of mercury. In this way, it was established that the oxidation of mercury to mercury (I) ions proceeds quantitatively with 100% current efficiency.     

Multiphase telomerisation of butadiene with acetic acid and acetic anhydride

Two different routes to acetoxyoctadiene are presented. The first one uses the well-known telomerisation of butadiene with acetic acid operating in a multiphase semi-batch mode. The second reaction involves the cleavage of acetic anhydride, hydrogen transfer via ketene formation and thus a telomerisation as well.     

Reactions of the radial cattions of acetic acid and acetic anhydride in CFCl3

The ESR spectra of -irradiated, at –196 °C, solutions of acetic acid and acetic anhydride were studied depending on their concentrations in CFCl₃. The structure of thus produced radical cations is confirmed with the deuterium substituted analogues. It has been shown that the ion-molecular reaction of the radical cation CH₂COOH⁺ in the isolated dimer takes place for the dilute solutions of acetic acid in CFCl₃ resulting in the formation of CH₃COO follwed by its decomposition to CH₃+CO₂ while the radicals CH₂COOH are formed via secondary processes. The reactions of radical cations of acetic oxide have been also studied.     

Non-photochemical laser-induced nucleation of supercooled glacial acetic acid

Non-photochemical laser-induced nucleation (NPLIN) of glacial acetic acid (GAA) is demonstrated. The fraction of samples nucleated depends linearly on peak laser power density at low powers (<100 MW cm(-2)) with a threshold of (9.0 ± 4.2) MW cm(-2); at higher laser powers the fraction reaches a plateau of 0.75 ± 0.24 (2σ uncertainties). A simple model based on polarizability of pre-nucleating clusters gives a value of the solid-liquid interfacial tension γ(SL) = 15.5 mJ m(-2). It is hoped that the results will stimulate new developments in experimental and theoretical studies of cluster structure and nucleation in liquids.     

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.     

Trifluoromethyl sulphonic acid as a titrant in glacial acetic acid systems

Trifluoromethyl sulphonic acid in glacial acetic acid has been compared with perchloric acid in glacial acetic acid as a titrant in a limited number of cases. It does not appear that the reagent is likely to compete seriously with perchloric acid in non-aqueous titrimetry. Although comparable to perchloric acid in acid strength in acetic acid as well as in instrument response, it is unlikely that the considerably higher cost can be justified on the grounds of freedom from precipitate formation alone and no other advantageous feature has been observed which could justify this.

Abstract

Trifluoromethylsulfonsäure in Eisessig wurde mit Perchlorsäure in Eisessig als Titrationsmittel verglichen. Es scheint nicht wahrscheinlich, dass das Reagens ernsthaft mit Perchlorsäure als Titrationmittel in nichtwässrigem Medium konkurrieren kann. Das Reagens ist zwar mit Perchlorsäure vergleichbar, soweit es die Stärke (in Essigsäure) und das Ansprechen des Instrumentes betrifft; es ist aber unwahrscheinlich, dass sich die beträchtlich höheren Kosten lediglich wegen Nichtauftretens von Niederschlägen rechtfertigen lassen. Dies ist der einzige auffindbare Vorteil.     

Kinetics and mechanism of triphenylphosphine quarternization with unsaturated carboxylic acids in the medium of acetic acid

Kinetics of reaction of triphenylphosphine with a series of unsaturated carboxylic acids and related esters in the medium of acetic acid as well as in mixtures of acetic acid and acetonitrile was studied by spectrophotometry. The data obtained show that the process of quarternization should be described by kinetic equation of third order, the proton transfer occurs from the solvent. A stepwise mechanism of interaction including formation of prereaction complex on the reaction pathway is proposed.     

Heat transfer in the desublimation of phthalic anhydride

The heat transfer in the desublimation of phthalic anhydride has been investigated experimentally for the purpose of modelling and developing the design calculation procedure.Experiments were performed on a pilot installation connected to the industrial plant. On the basis of the experimental data, new correlations for the equivalent local heat transfer resistance and the mean equivalent density of the condensate were obtained. The formula for the equivalent heat transfer coefficient in the gaseous phase and the diagram for determination of the efficiency of the process are also given. The validity of the proposed formulae was verified by comparison of the calculated temperature profiles along the condenser with the measured values.     

Kinetics and mechanism of oxidation of 4-oxoacids by N-bromosuccinimide in aqueous acetic acid medium

Kinetics and mechanism of oxidation of substituted and unsubstituted 4-oxoacids (S) by N-bromosuccinimide (NBS) in aqueous acetic acid medium have been studied potentiometrically. The reaction follows first-order kinetics, each in 4-oxoacids, NBS and H⁺. The effect of changes in the electronic nature of the substrate reveals that there is a development of positive charge in the transition state. Based on the kinetic results and the product analysis, a suitable mechanism has been proposed for the reaction of NBS with 4-oxoacids.     

Potentiometric determination of urea with perchloric acid in acetic anhydride

A potentiometric method for the quantitative determination of urea is proposed. Urea is titrated with perchloric acid in acetic anhydride solvent. This method is rapid and less costly than the semi-micro Kjeldahl method. In addition, its accuracy is nearly identical with that of Kjeldahl's method. An analysis of a given sample is completed in about 30 min.     

Reactions of lycoctonine alkaloids with acetic anhydride and p-toluenesulfonic acid

The reactions of alkaloids having a 7,8-diol system — lycoctonine, browniine, and dihydromonticoline — with acetic anhydride and p-toluenesulfonic acid have been studied. The optimum conditions for this reaction, leading to anhydro compounds, have been found.Abuali ibn Sino [Avicenna] Tadzhik State Medical Institute, Dushanbe; Institute of Chemistry, Baskir Scientific Center, Urals Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 545–547, July–August, 1991.     

Iodine trichloride in glacial acetic acid as an oxidizing titrant

A systematic study of the redox reactions of iodine trichloride with various inorganic ions in glacial acetic acid medium is described. Sodium sulphite, arsenic trichloride, antimony trichloride, iron(II) perchlorate and mecury(I) perchlorate were examined. Potentiometric and amperometric methods were used to follow the reduction of iodine trichloride, which yields different products according to the type of reductant.     

Kinetics and mechanism of the additive reaction of aniline with dicyandiamide

Kinetics of the additive reaction of aniline with dicyandiamide resulting in phenylbiguanide production was studied based on the analysis of reaction rate by high performance liquid chromatography. It is a second-order reaction on the condition of the constant temperature and acidity. It is first-order for both aniline and dicyandiamide. The reaction rate is influenced evidently by acidity. It reaches its maximum at pH 2.6. The mechanism for this reaction was suggested that aniline is nucleophilic reagents additive with the protonated cyano-group in dicyandiamide. The rate equation derived from the mechanism can describe the experimental results well. The reaction rate calculated from the rate equation reaches its maximum at pH 2.5, which is close to the experimental result. For different aromatic amine adding to dicyandiamide have the same reaction order, the mechanism ought to be the same. Published in Russian in Kinetika i Kataliz, 2009, Vol. 50, No. 3, pp. 379–385. The article is published in the original.     

Kinetics and products of the reactions of ozone with toluene and its derivatives in acetic anhydride

The reactions of ozone with toluene and its derivatives in acetic anhydride were studied. It was found that competing parallel reactions of ozone with the aromatic ring and substituents occurred in the ozone-arene-acetic anhydride system. The ratio between these reaction paths depended on the arene structure and reaction conditions. The selectivity of the oxidation of toluene and its derivatives at the methyl group varied from 0 to 40%. The fraction of aromatic products decreased as the number of methyl groups at the ring was increased. Tri- and tetramethylbenzenes were oxidized only at the aromatic ring. The stability of an aromatic system increased upon the introduction of electron-acceptor substituents into the benzene ring. Aminotoluenes and hydroxytoluenes were oxidized with ozone mainly at the NH₂ and HO groups; however, as in the case of toluene, the aromatic ring and methyl group became the main directions upon their acylation. The oxidation of the methyl group in acetic anhydride in the presence of sulfuric acid was finished at the step of the formation of the acylated derivatives of benzyl alcohols and benzaldehydes, which are resistant to the action of ozone.