Influence of unsaturated aliphatic and aromatic volatile organic compounds on the oxidation of aqueous sulfur dioxide by oxygen in aqueous medium

The trace atmospheric volatile organic compounds(VOCs) are reported to influence the oxidation of dissolved sulfur dioxide, S(IV), by oxygen, which is an important reaction in atmospheric acid formation. In this work, the influence of 15 VOCs on uncatalyzed oxidation of S(IV) by oxygen has been investigated by following the disappearance of [O₂]. The inhibition of oxidation reaction by toluene, aniline, benzene, cinnamic acid, hydroquinone, acrylamide, acrylonitrile and allyl alcohol was defined by the rate law(A):k_VOC = k₀/(1+B [Inh]) (A)where, k_VOC, and k₀ are the first order rate constants in the presence and the absence of VOCs respectively. B is the inhibition parameter and [Inh] is the concentration of inhibitor.On the other hand, fumaric, maleic and crotonic acids, which have conjugated CC bonds, catalyze the reaction defined by the rate law(B):k_VOC = k₀ + k_cat [VOC] (B)where k_cat is catalytic constant and [VOC] is the concentration of catalytic VOC.Interestingly, presence of 1-hexene, cyclohexene, methacrylic acid, methyl acrylate was without any significant effect on the rate of reaction.     

Effect of anions on the oxidation of organic compounds with ultrasonically activated persulfate

The effect of anions typically present in natural and waste waters on the oxidation of the azo dye methyl orange with persulfate activated with high-frequency ultrasound was studied. At a chloride concentration of 1 mmol/L, the rate constant of substrate oxidation increased 1.5-fold, but further increase in the chloride content retarded the process. The addition of nitrates, carbonates, and hydrogen carbonates to the solution inhibited the process (NO₃^- < HCO₃^- ~ CO₃^2-). These tendencies were in good agreement with the results obtained on a real water matrix of the natural surface water from Lake Baikal.     

Kinetic features of ammonium persulfate decomposition in aqueous medium

Russian Chemical Bulletin - Decomposition of ammonium persulfate in an aqueous medium (353–368 K) is limited by decomposition of persulfate ions with a rate constant logk 2 =...     

Iodometric microdetermination of sulphur in organic compounds by an amplification reaction

A new method is described for the iodometric microdetermination of sulphur in organic compounds, using a 12-fold amplification reaction after oxygen-flask combustion. The method is based on reaction of the resulting sulphuric add with an excess of saturated barium bromate solution. The unreacted barium bromate is precipitated by addition of acetone, filtered off, redissolved in hot water and after addition of an excess of iodide and acid, the iodine liberated is titrated with thiosulphate. The method is simple, rapid, highly accurate, and of wide application in the microanalysis of organosulphur compounds containing other common acid-forming elements.     

Benzoin reaction in water as an aqueous medium catalyzed by benzimidazolium salt

Benzoin reactions are catalyzed by N,N-dialkylbenzimidazole to yield α-hydroxy ketones; the reaction proceeds in water as an aqueous medium under mild conditions. The utility of these salts as pre-catalysts in these reactions has been demonstrated.     

Influence of a reaction medium on the oxidation of aromatic nitrogen-containing compounds by peroxyacids

The influence of different solvents on the oxidation reaction rate of pyridine (Py), quinoline (QN), acridine (AN), α-oxyquinoline (OQN) and α-picolinic acid (APA) by peroxydecanoic acid (PDA) was studied. It was found that the oxidation rate grows in the series Py < QN < AN, and the rate of the oxidation reaction of compounds containing a substituent in the α position from a reactive center is significantly lower than for unsubstituted analogues. The effective energies of activation of the oxidation reaction were found. It was shown that in the first stage, the reaction mechanism includes the rapid formation of an intermediate complex nitrogen-containing compound, peroxyacid, which forms products upon decomposing in the second stage. A kinetic equation that describes the studied process is offered. The constants of equilibrium of the intermediate complex formation (K _eq) and its decomposition constant (k ₂) in acetone and benzene were calculated. It was shown that the nature of the solvent influences the numerical values of both K _p and k ₂. It was established that introduction of acetic acid (which is able to form compounds with Py) into the reaction medium slows the rate of the oxidation process drastically. Correlation equations linking the polarity, polarizability, electrophilicity, and basicity of solvents with the constant of the PDA oxidation reaction rate for Py were found. It was concluded that the basicity and polarity of the solvent have a decisive influence on the oxidation reaction rate, while the polarizability and electrophilicity of the reaction medium do not influence the oxidation reaction rate.     

Multifunctional bioconjugation by Morita-Baylis-Hillman reaction in aqueous medium

An efficient approach for modular assembly of multifunctional bioconjugates from oligosaccharides, peptides and proteins with fluorescent probes/affinity tags based on Morita-Baylis-Hillman (MBH) reaction in aqueous medium has been developed.     

Aerobic oxidation of organic compounds catalyzed by vanadium compounds

Aerobic oxidation of α-hydroxy ketones catalyzed by dichloroethoxyoxovanadium in ethanol causes a carbon–carbon bond cleavage that produces diesters or diketones. This reaction is highly chemoselective, and disecondary glycols do not react at all. However, ditertiary glycols effectively react with dichloroethoxyoxovanadium or trichlorooxovanadium to provide the corresponding ketones. Aerobic oxidation of α-hydroxy ketones catalyzed by dichloroethoxyoxovanadium or trichlorooxovanadium in aprotic solvents almost quantitatively affords the corresponding α-diketones. The reaction of tertiary cyclopropanol compounds with vanadyl acetylacetonate under an oxygen atmosphere causes fragmentation of the cyclopropane moiety to produce β-hydroxy ketones and β-diketones. For the 6-substituted bicyclo[4.1.0]heptanol derivatives, the endoperoxides are also obtained together with β-hydroxy ketones. Conversely, 2-ethoxycarbonylcyclopropyl silyl ethers produce γ-oxocarboxylate derivatives given the same reaction conditions. Monothioacetals are easily deprotected into carbonyls using a catalytic amount of trichlorooxovanadium in 2,2,2-trifluoroethanol under an oxygen atmosphere. Thiols are converted into the corresponding disulfides by the aerobic oxidation catalyzed by trichlorooxovanadium in the presence of molecular sieves 3A. Polymer-supported vanadium compounds are synthesized by the reaction of vanadium oxytrichloride with polymers bearing hydroxyl moieties. The catalyst prepared from TentaGel S OH was highly active and reusable for the aerobic oxidations.     

Air oxidation of organic compounds in aqueous solutions. Ecochemical and analytical aspects

The results of static and dynamic laboratory experiments confirm the oxidation of organic compounds in aquatic medium by dissolved oxygen of atmospheric air to be possible under conditions close to normal. Alkylaromatics containing hydrogen atoms in alkyl substituents in α-positions to the aromatic system, as well as simple ethers, are characterised by the highest chemical reactivity in relation to triplet (³Σ _g ^? ) which is consistent with the pattern of free-radical reactions. Principal environmental and analytical consequences of the obtained results are under discussion. Liquid-phase free-radical reactions of atmospheric oxygen may proceed with the participation of atmospheric aerosols, i.e water droplets within clouds. Another example relates to the prevention of accumulation in natural bodies of water stable nonylphenol (predominantly 4-tert-isomers), characterized by endocrine activity. Suggested the possibility of replacing them with secondary alkylphenols, identical in all chemical properties except for the ease of oxidation by air oxygen in aqueous solutions     

Highly enantioselective organocatalytic direct aldol reaction in an aqueous medium

We have demonstrated that small organic molecules 1 and 2 catalyzed the direct aldol reaction of both acyclic and cyclic ketones with different aldehydes in an excess of water/brine. Excellent enantioselectivities up to >99% and diastereoselectivities up to 99% with very good yields were obtained by using much lower catalyst loadings (0.5 mol %).     

An efficient one-pot synthesis of tetrahydroquinoline derivatives via an aza Diels-Alder reaction mediated by CAN in an aqueous medium and oxidation to heteroaryl quinolines

Various tetrahydroquinoline derivatives have been synthesized by employing ceric ammonium nitrate in an aqueous medium. Subsequently, the tetrahydroquinolines were oxidized to biheterocycles.     

A chemoselective aerobic oxidation of benzylic azides catalyzed by molybdenum xanthate in an aqueous medium

A mild molybdenum-catalyzed, aerobic, chemoselective oxidation of benzylic azides to the corresponding aldehydes in an aqueous medium that tolerates a variety of functional groups including alcohols, esters, ketones, halides and olefins is described.     

Radical polymerization as an indicator reaction for determination of organic compounds

Polymerization of methyl methacrylate (MMA) and 4-vinylpyridine (VP) has been carried out in an aqueous solution in the presence of the initiating system persulfate-tetramethylethylenediamine. The reaction rate has been monitored by measuring the light absorbance of the suspension of the resulting polymer. The effect of 26 model organic compounds on the polymerization rate has been studied. It has been shown that the VP polymerization is inhibited by a smaller number compounds (9 compounds) than the MMA polymerization (22 compounds), which indicates that the former reaction has better selectivity, whereas the determination of model compounds using the MMA polymerization reaction is more sensitive. This is explained by the lower chain growth rate constant for VP vs. MMA and different stationary concentrations of radicals in the systems. The use of these indicator polymerization reactions makes it possible to distinguish some closely related compounds, e.g., 1,4-benzoquinone and 9,10-anthraquinone (MMA reaction) or dinitrophenol and 4-nitrophenol or phenol (VP reaction). Determination of ascorbic acid in a pharmaceutical formulation has been carried out.     

The oxidation of organic compounds

In a study of the behavior of tris(hydroxymethyl)-4-picoline (I) under the conditions of vapor-phase oxidation on a vanadium-tin oxide catalyst, it was found that with the addition of 150–250 mole of water and 125–200 mole of O₂ per mole of I and a contact time of 0.35–0.45 sec, the main reaction product was isonicotinic acid (II), the yield of which amounted to 60–65% of theoretical, calculated on the I passed.For part XLVIII, see [1].     

Chiral nematic phase formation by aqueous suspensions of cellulose nanocrystals prepared by oxidation with ammonium persulfate

There is continuing interest in the growing family of nanocellulosic materials prepared from plant cell wall material. While most of the research on cellulose nanocrystals has focused on the product of sulfuric acid hydrolysis stabilized by surface sulfate half-esters, cellulose nanocrystals with surface carboxyl groups have also been prepared by oxidation of lignocellulosic materials with ammonium persulfate. The major difference is that the persulfate oxidation leads to nanocrystals stabilized by surface carboxyl groups. Some properties of cellulose nanocrystals from cotton and wood, prepared by persulfate oxidation, are compared with those observed for nanocrystals prepared by sulfuric acid hydrolysis. Evidence from polarized light microscopy showed that the nanocrystal suspensions prepared by persulfate oxidation also form chiral nematic ordered phases in water.