Autoxidation of polypropylene catalyzed by cobalt salt in the liquid phase

The autoxidation of isotactic polypropylene suspended in the organic solvent was found to proceed very rapidly in the presence of cobalt salts. The rate of oxidation increases and the induction period decreases as the concentration of the cobalt is increased. The rate of oxidation depends on solvent and is quite fast in fatty acids. Polypropylene has shown a rapid decrease in molecular weight at the initial stage of oxidation, and the volatile products were mainly composed of carbon dioxide and small amount of carbon monoxide. Other oxidation products were acetic acid-soluble resinous materials, having molecular weights of 250–730, with a molar ratio of carbon to oxygen of 3.0–5.4. Atactic polypropylene, relatively stable against oxidation, was oxidized easily in the presence of cobalt and bromide ion. The difference in the rate of oxidation depending on the tacticity of polypropylene is attributed primarily to steric hindrance to the intramolecular hydrogen abstraction step.     

Autoxidation of 2-mercaptoethanol catalyzed by cobalt(II) phthalocyaninetetrasulfonate on colloidal particles

Cobalt(II) phthalocyaninetetrasulfonate (CoPcTS) is a highly active catalyst in aqueous media for the autoxidation of thiols to disulfides, and cationic polymers further enhance the activity. In this work we tested a variety of cationic polymer supports for the CoPcTS-catalyzed autoxidation of 2-mercaptoethanol in aqueous dispersions at 25°C. The order of activities is cationic polyelectrolytes > cationic polymer colloids > cationic colloidal silica > aqueous solution > ion exchange resins. Spectroscopic studies indicate that the high activity of the polyelectrolytes correlates with their ability to aggregate the CoPcTS. © 1992 John Wiley & Sons, Inc.     

Iron catalyzed demethylation of acetic acid*

Abstract

The iron(IV)-oxo catalyzed cleavage of acetic acid is reported. Iron(II) complexes are used as catalyst precursors and H₂O₂ as oxidant in reactions in aqueous solution with an excess of chloride and, in some experiments, with ascorbic acid added as an OH^. radical scavenger. It is shown that the acetic acid is cleaved into CO₂ and a methyl radical. In the presence of O₂ and OH^. radicals, the initially generated methyl radicals produce methanol and formate. Halogenated alkanes are also formed and, in the absence of O₂ and OH^. radicals, methane is obtained as the major product. A mechanism for the formation of various environmentally important volatile C₁ compounds is deduced from the present results and published studies, and its relevance as an additional source for these compounds in the atmosphere is discussed.     

Asymmetric hydrogenation of salicyl alcohol catalyzed by methylsulfo–sodium carboxymethylcellulose–Pt complex

A new chiral polymer–metal complex, methylsulfo–sodium carboxymethyl–cellulose–Pt complex (MS‐NaCMC‐Pt), has been prepared by the reaction of sodium carboxymethylcellulose with methylsulfonyl chloride and H₂PtCl₆·6H₂, which was found to be able to catalyze the asymmetric hydrogenation of salicyl alcohol to give (1S,2S)‐2‐(hydroxymethyl)‐cyclohexanol at 28 °C and under 1 atm H₂, in > 90% product and optical yields, respectively. The catalyst could be reused many times without any remarkable changes in optical catalytic activity. Copyright © 2000 John Wiley & Sons, Ltd.     

Addition of acetic acid to styrene catalyzed by ion exchanger

The possibility of preparation of 1-phenylethyl acetate by direct addition of acetic acid to styrene catalyzed by Ostion KS in the acid cycle has been investigated. The reaction is accompanied by the formation of higher molecular compounds. The effect of temperature, mole ratio of the starting compounds, stabilization of styrene, amount of the catalyst and of its repeated use on the reaction rate and selectivity of the process has been examined. In the case of some economic application of higher-molecular side products the process could be used on a technical scale.

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Equilibrium and kinetics studies of reactions of manganese acetate, cobalt acetate, and bromide salts in acetic acid solutions

The oxidation of hydrogen bromide and alkali metal bromide salts to bromine in acetic acid by cobalt(III) acetate has been studied. The oxidation is inhibited by Mn(OAc)(2) and Co(OAc)(2), which lower the bromide concentration through complexation. Stability constants for Co(II)Br(n)() were redetermined in acetic acid containing 0.1% water as a function of temperature. This amount of water lowers the stability constant values as compared to glacial acetic acid. Mn(II)Br(n)() complexes were identified by UV-visible spectroscopy, and the stability constants for Mn(II)Br(n)() were determined by electrochemical methods. The kinetics of HBr oxidation shows that there is a new pathway in the presence of M(II)Br(n)(). Analysis of the concentration dependences shows that CoBr(2) and MnBr(2) are the principal and perhaps sole forms of the divalent metals that react with Co(III) and Mn(III). The interpretation of these data is in terms of this step (M, N = Mn or Co): M(OAc)(3) + N(II)Br(2) + HOAc --> M(OAc)(2) + N(III)Br(2)OAc. The second-order rate constants (L mol(-)(1) s(-)(1)) for different M, N pairs in glacial acetic acid are 4.8 (Co, Co at 40 degrees C), 0.96 (Mn, Co at 20 degrees C), 0.15 (Mn(III).Co(II), Co at 20 degrees C), and 0.07 (Mn, Mn at 20 degrees C). Following that, reductive elimination of the dibromide radical is proposed to occur: N(III)Br(2)OAc + HOAc --> N(OAc)(2) + HBr(2)(*). This finding implicates the dibromide radical as a key intermediate in this chemistry, and indeed in the cobalt-bromide catalyzed autoxidation of methylarenes, for which some form of zerovalent bromine has been identified. The selectivity for CoBr(2) and MnBr(2) is consistent with a pathway that forms this radical rather than bromine atoms which are at a considerably higher Gibbs energy. Mn(OAc)(3) oxidizes PhCH(2)Br, k = 1.3 L mol(-)(1) s(-)(1) at 50.0 degrees C in HOAc.     

十六烷基三甲基溴化铵催化合成间甲苯氧乙酸

<正>植物生长调节剂系人工合成具有天然植物激素活性的物质。芳氧乙酸及其酯类是一种具有多种用途的选择性除莠剂,同时也是植物的生长调节剂和除草剂[1]。研究探讨合成芳氧乙酸的新技术以提高生产能力,对工农业生产有着重要的现实意义。制备芳氧乙酸一般采用Williamson法、     

Esterification reaction kinetics of acetic acid and n-pentanol catalyzed by sulfated zirconia

This study reports experimental data and kinetic modeling of acetic acid esterification with n-pentanol using sulfated zirconia as a catalyst. Reactions were carried out in an isothermal well-mixed batch reactor at different temperatures (50-80°C), n-pentanol to acid molar ratios (1:1-3:1), and catalyst loadings (5-10 wt% in relation to the total amount of acetic acid). The reaction mechanism regarding the heterogeneous catalysis was evaluated considering pseudo-homogeneous, Eley–Rideal, and Langmuir–Hinshelwood model approaches. The reaction mixture was considered a nonideal solution and the UNIQUAC thermodynamic model was used to take into account the nonidealities in the liquid phase. The results obtained indicated that increases in the temperature and catalyst loading increased the product formation, while changes in the n-pentanol to acetic acid molar ratio showed no significant effect. The estimated enthalpy of the reaction was −8.49 kJ mol⁻¹, suggesting a slightly exothermic reaction. The Eley–Rideal model, with acetic acid adsorbed on the catalyst as the limiting step, was found to be the most significant reaction mechanism.     

Diffusion of water–acetic acid mixtures in epoxy

The solubility and diffusion of water–acetic acid solutions in epoxy resins has been studied by nuclear magnetic resonance imaging (MRI) and spectroscopy (NMR), Fourier transform infrared (FTIR) spectroscopy, and light microscopy (LM). These techniques revealed the progression of a sharp diffusion front at a rate proportional to the square root of time. Both the swelling and rate of diffusion are dependent on acid dilution. At higher acid concentrations, hydrogen bonds were present, which has been interpreted as formation of acid dimers. The results indicate that molecular interactions play a major role in controlling the solubility and diffusion processes. The observation that voids can be filled up with penetrant strongly support the interpretation that molecular interactions rather than concentration gradient are responsible for these effects. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 3328–3336, 1999     

Mechanism of transesterification and cyclization of epoxy–polycarbonate blends catalyzed by quarternary ammonium salt

The reaction of oxirane with carbonate using quarternary ammonium salts as catalyst has been studied. Curing is caused by the transesterification reaction of the oxirane cycle with the carbonate group that proceeds by an “insertion” mechanism in the stoichiometric system. The ratio of the reactants is two oxirane groups to one carbonate group. In the nonstoichiometric system, the epoxide content is more than the stoichiometric quantity required. A cyclization reaction is followed by the transesterification reaction. To identify the finished products, a model reaction was proposed using diphenyl carbonate and phenyl glycidyl ether which results in the formation of 4-phenoxymethyl-1,3-dioxolane-2-one (PMD). The mechanism of forming the cyclic structure is assumed to proceed through the chain scission of the network in which the molecular chain crosslinked with carbonate group by a transesterification reaction. © 1996 John Wiley & Sons, Inc.     

Reactivity of cobaloxime bound to polystyrene chain by carbon–cobalt σ bond

The (alkyl)-bis(dimethylglyoximato)pyridinecobalt attached to polychloromethylstyrene by a cobalt–carbon bond was prepared by the reaction of Co(II)(DH)₂Py with polychloromethylstyrene in benzene. The fraction of p-vinylbenzyl·Co(DH)₂Py introduced to the polymer was 8.1 and 2.1 mole %. The photodecomposition of the polymer-bonded cobaloxime was investigated by following the change of the visible spectrum. The rate constant k_dec of the polymer-bonded cobaloxime was 1.1 × 10^?2 sec^?1 in benzene; it is one-fourth of that of its monomeric analog, benzyl·Co(DH)₂Py. The k_dec values of the cobaloximes were also measured in benzene–dimethyl sulfoxide mixed solvents, and the polymer effects were discussed. The dependence of the photodecomposition on energy of the irradiation light was investigated, and it was found that the absorption band near 470 nm is important for the photodecomposition of the cobalt–carbon bond. Spectroscopic measurements of the ligand exchange reaction of polymer-bonded cobaloxime with pyridine in dimethyl sulfoxide gave a larger equilibrium constant (1.2 × 10⁴ liter/mole) than that of benzyl·Co(DH)₂Py (9.4 × 10² liter/mole). The kinetic data of the ligand exchange reaction indicated that the larger equilibrium constant for the polymeric system is due to the smaller rate constant of the reverse reaction. The thermodynamic parameters were also obtained.     

Synthesis and characterisation of cobalt complex of sulfathiazole with acetic acid

The synthesis and characterization of the Co(II) complex of sulfathiazole is presented here. The compound was characterised by spectroscopic methods and crystal structure of the complex was determined as well. The complex crystallizes in the triclinic crystal form with the space group of $\overline{P_1}$. The asymmetric unit of the title compound contains one tetrachlorocobaltate anion, two sulfathiazolium cations and one acetic acid molecule in the crystal lattice. The Co(II) ion exhibits tetrahedral environment surrounded by four chloride ions. The two sulfathiazolium cations are linked by O–H···N hydrogen bonds.     

Oxidative aromatization of Hantzsch 1,4-dihydropyridines by aqueous hydrogen peroxide-acetic acid

A simple method for the oxidative aromatization of Hantzsch 1,4-dihydropyridines to the corresponding pyridines is achieved by using hydrogen peroxide as green oxidant and acetic acid as catalyst in aqueous solution.     

The salt effect in the alkaline hydrolysis ofO-ethylO-(p-nitrophenyl) chloromethylphosphonate catalyzed by cetylpyridinium bromide

The alkaline hydrolysis ofO-ethylO-(p-nitrophenyl) chloromethylphosphonate catalyzed by the micelles of cetylpyridinium bromide is inhibited on addition of KCl, K Br, or sodium salicylate (NaSal). This is caused by both a decrease in the nucleophile concentration in micelles owing to a reduction in the surface potential and a change in the micellar structure and properties. Dedicated to the memory of Academician M. I. Kabachnik in connection with his 90th anniversary. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1922–1926, October, 1998.     

Alternating copolymerization of carbon dioxide and epoxide catalyzed by an aluminum Schiff base–ammonium salt system

The alternating copolymerization of carbon dioxide (CO₂) and cyclohexene oxide (CHO) with an aluminum Schiff base complex in conjunction with an appropriate additive as a novel initiator is demonstrated. A typical example is the copolymerization of CO₂ and CHO with the (Salophen)AlMe ( 1a )–tetraethylammonium acetate (Et₄NOAc) system. When a mixture of the 1a –Et₄NOAc system and CHO was pressurized by CO₂ (50 atm) at 80 °C in CH₂Cl₂, the copolymerization of CO₂ and CHO took place smoothly and produced a high polymer yield in 24 h. From the IR and NMR spectra, the product was characterized to be a copolymer of CO₂ and CHO with an almost perfect alternating structure. The matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry analysis indicated that an unfavorable reaction between Et₄NOAc and CH₂Cl₂ and a possible chain‐transfer reaction with concomitant water occurred, and this resulted in the bimodal distribution of the obtained copolymer. With carefully predried reagents and apparatus, the alternating copolymerization in toluene gave a copolymer with a unimodal and narrower molecular weight distribution. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4172–4186, 2005     

Potassium bromide or sodium chloride catalyzed acetoxyselenenylation of alkenes with diselenides and mCPBA

KBr or NaCl is found to be a good catalyst in Se-Se bond cleavage of diselenides in the present of the oxidant mCPBA. The electrophilic addition of the in situ generated reactive electrophilic selenium species PhSeX (X=Br, Cl) to alkenes in AcOH provides a convenient access to 2-acetoxy-1-selenides. Compared with other catalysts, KBr or NaCl is less expensive and more environment-friendly.     

Spectral and thermal characterization of polyaniline–oxalic acid salt

Polyaniline–oxalic acid salts were prepared at 5 and 30°C by chemical polymerization of aniline using different concentration of oxalic acid. Polyaniline base was obtained from the corresponding polyaniline salt by dedoping using aqueous ammonium hydroxide solution. Conductivity measurements, elemental analysis, Infrared, electronic absorption, electron paramagnetic resonance spectral, and thermogravimetric analysis were performed on the polyaniline salts and bases. Composition and the extent of dopant in polyaniline salt systems where determined. The value of composition of polyaniline: oxalic acid is 4: 1.6 and the polymer yield is around 66%. The value of conductivity, polymer yield and composition of polyaniline–oxalic acid salt is independent of concentration of oxalic acid used and also the synthesis temperature. The results are compared with polyaniline–hydrochloride salt prepared by chemical polymerization. The conductivity of polyaniline–oxalic acid salt is three orders of magnitude lower than that of polyaniline-hydrocholoride salt. © 1995 John Wiley & Sons, Inc.