Peroxidation, polycyclic

It is understandable that dihydro adducts should be formed by polycyclic compounds and not by benzene or pyridine, because the loss of aromatic resonance energy is smaller in the former than in the latter process, (c) When dibenzoyl peroxide is decomposed in very dilute solution (0.01 Af) in benzene, 1,4-dihydro biphenyl is produced as well as biphenyl, consistent with addition of the phenyl... 

The metabolic activity of other white-rot fungi including Phanerochaete chrysosporium and Pleurotus ostreacus has been discussed in the context of polycyclic aromatic hydrocarbons. For example, the mineralization potential of the manganese peroxide system fmmNematolomafrowardii for a number of substrates has been demonstrated (Hofrichter et al. 1998) the formation of CO2 from labeled substrates ranged from 7% (pyrene) to 36% (pentachlorophenol), 42% (2-amino-4, 6-dinitrotoluene), and 49% (catechol). 

In addition to the parent compound 2, the derivatives 2a, b, the benzo-system 16, the lactone-peroxides 17, and the fused polycyclic derivatives 18 and 19 could be prepared via the singlet oxygen-diimide route. For example, the parent system 2 was obtained in ca. 40% yield by diimide reduction of the stable 1,3-cyclohexadiene endoperoxide in MeOH at 0 °C27,28). Dihydroascaridole 2a and dihydroergosterol endoperoxide... 

Ortiz Leon, M. Velasco, L., and Vazquez-Duhalt, R., Biocatalytic Oxidation of Polycyclic Aromatic-Hydrocarbons by Hemoglobin and Hydrogen-Peroxide. Biochemical and Biophysical Research Communications, 1995. 215(3) pp. 968-973. 

Peroxyoxalate-based CL reactions are related to the hydrogen peroxide oxidation of an aryl oxalate ester, producing a high-energy intermediate. This intermediate (l,2-dioxetane-3,4-dione) forms, in the presence of a fluorophore, a charge transfer complex that dissociates to yield an excited-state fluorophore, which then emits. This type of CL reaction can be used to determine hydrogen peroxide or fluorophores including polycyclic aromatic hydrocarbons, dansyl- or fluores-camine-labeled analytes, or, indirectly, nonfluorescers that are easily oxidized (e.g., sulfite, nitrite) and quench the emission. The most widely used oxalate... 

The carcinogenicity of polycyclic aromatic compound-rich tyre extender oils has lead to the proposal of a legislative ban on their use in Europe. The suitability of naphthenic oils as non-toxic plasticisers in tyre treads is discussed and results are presented of experimental studies of the use of these plasticisers in SBR, EPDM, sulphur-cured EPDM and peroxide-cured EPDM. Despite their low aromatic content, the naphthenic plasticisers are shown to give good results in SBR, probably as a result of the contribution to solvent characteristics of the naphthenic molecular structure. The use of naphthenic oils is expected to increase worldwide as they are said to be one of the best alternatives to aromatic extracts with regard to solvent properties, compatibility, performance and availability. 

Highly selective formation of phenyl acetate was observed in the oxidation of benzene with palladium promoted by heteropoly acids.694 Lead tatraacetate, in contrast, usually produces acetoxylated aromatics in low yields due to side reac-tions. Electrochemical acetoxylation of benzene and its derivatives and alkoxylation of polycyclic aromatics789 790 are also possible. Thermal or photochemical decomposition of diacyl peroxides, when carried out in the presence of polycyclic aromatic compounds, results in ring acyloxylation.688 The less reactive... 

Dioxiranes are three-membered cyclic ring peroxides that are expected to be very unstable owing to ring strain. They are effective oxygenating agents for epoxidations of olefins, allenes, polycyclic aromatic hydrocarbons, enols. and a, /i-unsaturated ketones for insertions of oxygen into X—H... 

During cooxidation, some substrates are activated to become more toxic than they were originally. In some cases substrate oxidation results in the production of free radicals, which may initiate lipid peroxidation or bind to cellular proteins or DNA. Another activation pathway involves the formation of a peroxyl radical from subsequent metabolism of prostaglandin G2. This reactive molecule can epoxidize many substates including polycyclic aromatic hydrocarbons, generally resulting in increasing toxicity of the respective substrates. 

An analogous reagent with an azido instead of a cyano group was generated in situ and used for the azidation of polycyclic hydrocarbons such as adamantane and norbomane catalysis by benzoyl peroxide was necessary, in refluxing chlorobenzene [17]. 

Ortiz-Leon M, Velasco L, Vazquez-Duhalt R (1995) Biocatalytic oxidation of polycyclic aromatic hydrocarbons by hemoglobin and hydrogen peroxide. Biochem Biophys Res Comm 215 968-973... 

Oxidizer Chemical substance that causes oxygen to combine with another chemical substance examples include oxygen and hydrogen peroxide Ozone depletion Destruction of the stratospheric ozone layer that protects the Earth from harmful effects of ultraviolet radiation. Depletion of ozone layer is due to the breakdown of certain chlorine- and/or bromine-containing compounds (chlorofluorocarbons or halons), which break down when they reach the stratosphere and then catalytically destroy ozone molecules Ozone layer Protective layer in the atmosphere, about 15 miles above the ground. The ozone layer absorbs some of the sun s ultraviolet rays, thereby reducing the amount of potentially harmful radiation that reaches the Earth s surface PAHs Polycyclic aromatic hydrocarbons... 

Thio analogs of these compounds, for example, PhP(S)(NHR)2 can also be prepared similarly, from the corresponding thiophosphonic halides and amines or by oxidative addition of sulfur to diaminophosphines, RP(NR92 Phenylphosphonic acid diamides, PhP(Q)(NHBu )2 (Q = S, Se) were prepared from PhP(NHBfr)2 by oxidative addition of sulfur or selenium and the 0x0 derivative PhP(0)(NHBu )2 by oxidation with tert-butyl peroxide. Their lithiation produces unusual cyclic or polycyclic dUithium salts of the phosphonate dianions [PhP(Q)(NBfr)2] (Q = O, S, Se). The dimethylaluminum derivatives PhP(Q)(NBu )2AlMe2 (Q = S, Se) obtained from PhP(Q)(NHBu )2 with AlMes are fom-membered chelate rings. ... 

Zard has developed the use of N-amidyl radicals. The precursors of the radical intermediates are 0-benzoyl hydroxyamines such as 37. Addition of a tributylstannyl radical to the carbonyl group of the benzoate moiety is followed by the cleavage of the weak N - O bond. A subsequent 5-exol6-endo tandem cyclization takes place to yield the skeleton of the natural product deoxyserratine (Scheme 12) [49]. Later, the same group disclosed a tin-free source of amidyl radicals that relies on the use of M-(0-ethyl thiocarbonyl-sulfanyl) amides and lauryl peroxide as initiator. Examples of polycyclization were also given [50]. On the occasion of a model study toward the synthesis of kirkine, the use of thiosemicarbazide precursors gave access to the tetracyclic structure of the natural product [51]. 

FFA = free fatty acids POV = Peroxide value PAH = polycyclic-aromatic hydrocarbons target figure for soybean oil target figures valid for max. tocopherol retention. 

Cziczo DJ, Thomson DS, Murphy DM (2001) Ablation, flux, and atmospheric implications of meteors inferred from stratospheric aerosol. Science 291 1772-1775 Dachs J, Eisemeich SJ (2000) Adsorption onto aerosol soot carbon dominates gas-particle partitioning of polycyclic aromatic hydrocarbons. Environ Sci Technol 34 3690-3697 Dalleska NF, Colussi AJ, Hyldahl AM, Hoffmaim MR (2000) Rates and mechanism of carbonyl sulfide oxidation by peroxides in concentrated sulfuric acid. J Phys Chem A 104 10794-10796 D Almeida GA, Schitz L (1983) Number, mass, and volume distributions of mineral aerosol and soils of the Sahara. J Clim Appl Meteorol 22 233-243... 

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