nitrophenols and phenoxy-radical

The gas-phase oxidation mechanism of phenol initiated by OH radical was investigated using DFT and ab initio calculations. The initiation of the reaction is dominated by OH addition to ortho-position, forming P2, which subsequently combines with O2 at the ipso-position to form P2-1-OO adduct. A concerted HO2 elimination process from P2-1-OO was found to be much faster than the common ring closure to bicyclic intermediates. The HO2 elimination process from P2-1-OO forms 2-hydroxy-3,5-cyclohexadienone (HCH) as the main product and is also responsible for the experimental fact that the rate constants for reaction between P2 and O2 are about 2 orders of magnitude higher than those between other aromatic-OH adducts and O2. It was speculated that HCH would isomerize to catechol, which is thermodynamically more stable than HCH and was the experimentally observed main product, possibly through heterogeneous processes. Reaction of P2 with NO2 proceeded by addition to form P2-n-NO2 (n = 1, 3, 5), followed by HONO elimination from P2-1/3-NO2 to form catechol. The barriers for HONO elimination and catechol formation are below the separate reactants P2 and NO2, being consistent with the experimental observation of catechol in the absence of O2, while H2O elimination from P2-1/3-NO2 to form 2-nitrophenol (2NP) is hindered by high barriers. The most likely pathway for 2NP is the reaction of phenoxy radical and NO2.

Topics: Atmosphere; Catechols; Gases; Hydroxyl Radical; Kinetics; Models, Chemical; Nitrogen Dioxide; Nitrophenols; Oxidation-Reduction; Phenol; Phenols; Quantum Theory; Thermodynamics

The stable radicals derived from different compounds were detected in process of styrene autopolymerization. The nitroxide radicals are produced from nitrosocompound, hindered hydroxylamine, nitrophenols and nitroanisoles. The phenoxyl radicals are formed from quinine methides, and naphtoxyl radicals are generated from 2-nitro-1-naphtol. The radicals are identified, the kinetics of their formation and follow-up evolution are studied. These radicals can participate in process of living radical polymerization as the mediators and can effect significantly on kinetics of polymerization and structure of the resulting polymer.

Topics: Anisoles; Electron Spin Resonance Spectroscopy; Free Radicals; Kinetics; Nitrogen Oxides; Nitrophenols; Nitroso Compounds; Phenols; Polymers; Styrene

The decomposition of peroxynitrite (PON) in aqueous solutions was investigated by monitoring the release of dioxygen as a function of pH together with the various reaction products generated from phenol. This substrate was used as a mechanistic model for tyrosine nitration in prostacyclin synthase for which we have reported a highly efficient nitration and inhibition by PON (Zou, M., Martin, C., and Ullrich, V. (1997) Biol Chem. 378, 707-713). Nitrite as a contaminant and product of PON generated 4-nitrosophenol and some nitrophenols in the acidic pH range. In the alkaline range high amounts of 4-nitrosophenol originated from the disproportionation of PON yielding dioxygen and NOx species. The hydroxylation of phenol occurred between pH 3 and 8 with a maximum at 4.5. The nitration by PON also required a pH between 4 and 8 but had a second maximum between 10 and 12, suggesting that in this pH range phenolate was the reacting species. All isomeric biphenols were found as dimerization products as well as 4-phenoxyphenol (4-hydroxydiphenyl ether), indicating phenoxy radicals as intermediates. Since anisol when incubated under the same conditions yielded only hydroxylation but virtually no nitration products, it was concluded that nitration of phenolic compounds requires a one-electron oxidation as a primary step, followed by addition of the nitrogen dioxide radical.

Topics: Anisoles; Free Radicals; Hydrogen-Ion Concentration; Kinetics; Molecular Structure; Nitrates; Nitrites; Nitrophenols; Oxygen; Phenol; Phenols; Tyrosine