Quinones reactions with ozone

Quinone exists in the atmosphere in the gas phase. The dominant atmospheric loss process for quinone is expected to be by reaction with the hydroxyl (OH) radical (reaction with ozone is expected to be slow because of the >C(0) substituent groups). The estimated half-life and lifetime of quinone in the atmosphere due to reaction with the OH radical are 3 and 4 h, respectively. Bolton JL, Trush MA, Penning TM, Dryhurst G, and Monks TJ (2000) Role of quinones in toxicology. Chemical Research in Toxicology 13 135-160. Monks TJ and Jones DC (2002) The metabolism and toxicity of quinones, quinoimines, quinone methides, and quinone-thioethers. Current Drug Metabolism 3 425 38. O Brien PJ (1991) Molecular mechanisms of quinone cytotoxicity. Chemico-Biological Interactions 80 1-14. 

Possible atmospheric reaction products are oxy-, hydroxy-, nitro- and hydroxynitro-PAH derivatives (Baek et al. 1991). Photochemical oxidation of a number of PAHs has been reported with the formation of nitrated PAHs, quinones, phenols, and dihydrodiols (Holloway et al. 1987 Kamens et al. 1986). Some of these breakdown products are mutagenic (Gibson et al. 1978). Reaction with ozone or peroxyacetyinitrate yields diones nitrogen oxide reactions yield nitro and dinitro PAHs. Sulfonic acids have also been formed from reaction with sulfur dioxide. 

Photolytic. Based on data for structurally similar compounds, acenaphthylene may undergo photolysis to yield quinones (U.S. EPA, 1985). In a toluene solution, irradiation of acenaphthylene at various temperatures and concentrations all resulted in the formation of dimers. In water, ozonation products included 1,8-naphthalene dialdehyde, 1,8-naphthalene anhydride, 1,2-epoxyacenaphthylene, and 1-naphthoic acid. In methanol, ozonation products included 1,8-naphthalene dialdehyde, 1,8-naphthalene anhydride, methyl 8-formyl-1-naphthoate, and dimethoxyacetal 1,8-naphthalene dialdehyde (Chen et al., 1979). Acenaphthylene reacts with photochemically produced OH radicals and ozone in the atmosphere. The rate constants and corresponding half-life for the vapor-phase reaction of acenaphthylene with OH radicals (500,000/cm ) at 25 °C are 8.44 x lO " cmVmolecule-sec and 5 h, respectively. The rate constants and corresponding half-life for the vapor-phase reaction of acenaphthylene with ozone at 25 °C are... 

ACETIC ACID, ETHENYL ESTER (108-05-4) Forms explosive mixture with air (flash point 18°F/-7°C). Polymerizes readily if not inhibited elevated temperatures, the influence of light, air, oxygen, water, or peroxides can initiate reaction. Must be stabilized (hydro-quinone or diphenylamine is recommended) to prevent polymerization. Violent reaction with strong oxidizers. Reacts with nonoxidizing mineral acids, strong acids, ammonia, aliphatic amines, alkanolamines, bases, azo compounds, oleum, ozone (forms explosive vinyl acetate... 

PROBABLE FATE photolysis dissolved portion should undergo rapid photolysis to quinones, when released to air, may undergo direct photolysis, although adsorption can slow this process, direct photolysis is important near surface of waters half-life for reaction with photo-chemically produced hydroxyl radicals 21.49 hr oxidation oxidation by chlorine and/or ozone could account for a small portion of the dissolved compound hydrolysis not an important process volatilization probably too slow to compete with adsorption as a transport process, evaporation may be important, but limited by adsorption, half-life 43 days sorption very strong adsorption onto suspended solids is the dominant transport process, adsorption in estuarine water 3 pg/L, 71% adsorbed on particles after 3 hr, after 3hr incubation in natural seawater, 75% of 2 pg/L adsorbed to suspended aggregates of dead photoplankton cells and bacteria biological processes bioaccumulation is short-term metabolization and microbial degradation are principal fates... 

PROBABLE FATE photolysis dissolved portion may undergo photolysis to quinones, potential for reaction with alkyl peroxy radicals and hydroperoxy radicals which are photo-chemically produced in humic waters, atmospheric and aqueous photolytic half-life 3.8-499 hrs oxidation if chlorine and/or ozone is present in sufficient quantity, rapid oxidation should occur, photooxidation half-life in air 1.1-11 hrs hydrolysis not an important process volatilization probably too slow to compete with adsorption as a transport process sorption dominant transport process, on land, it is strongly adsorbed to soil, remains in the upper soil layers, in water it will adsorb to sediments and particulate matter in the water column biological processes bioaccumulation is short-term accompanied by metabolization, microbial biodegradation is the dominant fate, biodegradation expected to be very slow (half-life 2 yrs with acclimated microorganisms)... 

PROBABLE FATE photolysis the dissolved portion of the compound may undergo rapid photolysis to quinones, atmospheric and aqueous photolytic half-lives 6 hrs-32.6 days, may be subject to direct photolysis in the atmosphere, reaction with photochemically produced hydroxyl radicals has a half-life of 1.00 days oxidation rapid oxidation by chlorine and/or ozone may compete for dissolved DBA, photooxidation half-life in air 0.428-4.28 hrs hydrolysis not an important process volatilization probably too slow to be important, rate uncertain sorption strong adsorption by suspended solids, especially organic particulates, should be the principal transport process biological processes bioaccumulation is short-term, metabolization and microbial biodegradation are the principal fates... 

Some aromatic compounds can also react with ozone, although most simple aromatic rings such as benzene derivatives and naphthalene do not. Anthracene reacts with ozone to give anthraquinone in 73% yield after an oxidative workup. Indeed, quinone formation is a more typical example of the reaction of ozone with aromatic compounds (for other oxidative cleavage reactions see sec. 3.8 and for oxidation to phenols and quinones see sec. 3.3). Only a reactive n bond, such as the 9,10 bond of phenanthrene, will oxidatively cleave, and phenanthrene (361) was oxidized to dialdehyde 362 upon treatment with ozone in methanol followed by a workup with potassium iodide in acetic acid. ... 

The kinetics and product distributions of ozonolysis of vinylcyclohexane and methylene cyclohexane have been investigated.162 Steric hindrance of the cyclic substituent largely offsets electronic effects hi determining the rate of reaction. The main products of ozonation of catechols were quinones, while catechol acetals gave rise to compounds with an opened benzene ring.163 The ozonolysis of azoles such as pyrroles, oxazoles, and imidazoles has been reviewed.164... 

Ozonolysis of 9,10-dibromo- (17a) and 9,10-dichloroanthracene (17b) was reported to occur partly by attack at the non-halogenated double bonds to yield the di- (18) and tetracarboxylic acids, 19, as well as by attack at the 9,10-positions to yield the dehalogenated product anthra-quinone, 22 (8). This dual attack might at first seem to be in contrast to what was said above about the relative rates of ozone attack at halo-genated and non-halogenated double bonds. However, this is not the case if one considers that (in analogy to the ozonolysis of the unsubstituted anthracene) the reaction at the 9,10-positions has to be formulated as an atom- rather than a bond attack. In accordance with such a rationalization, the authors (8) formulated the intermediates 20 and 21 as precursors for anthraquinone. 

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