Aromatic hydroxyl radicals with

Lloyd, A.C., Darnall, K.R., Winer, A.M., Pitts, Jr., J.N. (1976) Relative rate constants for reaction of the hydroxyl radical with a series of alkanes, alkenes, and aromatic hydrocarbons. J. Phys. Chem. 80, 189-794. 

Ohta, T., Ohyama, T. (1985) A set of rate constants for the reactions of hydroxyl radicals with aromatic hydrocarbons. Bull. Chem. Soc. Jpn. 58, 3029-3030. 

Perry, R.A., Atkinson, R., Pitts, J.N. (1977) Kinetics and mechanisms of the gas phase reaction of the hydroxyl radicals with aromatic hydrocarbons over temperature range 296 473 K. J. Phys. Chem. 81, 296-304. 

Gierer, J., Yang, E. and Reitberger, T. (1992). The reactions of hydroxyl radicals with aromatic rings in lignins, studied with creosol and 4-methylveratrol. Holzforschung, 46(6), 495-504. 

The aromatic-hydroxyl radical reaction has been studied by Davis et They reported rate constants for benzene and toluene and concluded that hydroxyl additions to the aromatic ring compete favorably with the abstraction of hydrogen atom from the alkyl substituent. Doyle et al recently published hydroxyl reaction rate constants for a series of alkylbenzenes. 

The effect of the hydroxyl radical (HO ) on luminol chemiluminescence has also been intensively studied Although detailed mechauisms for the reactiou of hydroxyl radicals with hydrazides remaiu uuknowu, two differeut processes are assumed to be involved oxidation of the hydrazide group and addition of hydroxyl radical to the aromatic ring (Scheme 19) ° . 

Rate constants for the reaction of hydroxyl radicals with different compounds were determined by Haag and Yao (1992) and Chramosta et al. (1993). In the study of Haag and Yao (1992) all hydroxyl radical rate constants were determined using competition kinetics. The measured rate constants demonstrate that OH0 is a relatively nonselective radical towards C-H bonds, but is least reactive with aliphatic polyhalogenated compounds. Olefins and aromatics react with nearly diffusion-controlled rates. Table 4-3 gives some examples comparing direct (kD) and indirect (kR) reaction rate constants of important micropollutants in drinking water. 

Rinke, M., Zetzsch, C. (1984) Rate constants for the reactions of hydroxyl radicals with aromatics benzene, phenol, aniline, and 1,2,4-trichlorobenzene. Ber. Bunsen-Ges. Phys. Chem. 88, 55-62. 

On the other hand, the indirect type of ozonation is due to the reactions of free radical species, especially the hydroxyl radical, with the organic matter present in water. These free radicals come from reaction mechanisms of ozone decomposition in water that can be initiated by the hydroxyl ion or, to be more precise, by the hydroperoxide ion as shown in reactions (4) and (5). Ozone reacts very selectively through direct reactions with compounds with specific functional groups in their molecules. Examples are unsaturated and aromatic hydrocarbons with substituents such as hydroxyl, methyl, amine groups, etc. [45,46],... 

Neta P, Dorfman LM. Pulse radiolysis studies. XIII. Rate constants for the reaction of hydroxyl radicals with aromatic compounds in aqueous solutions. Adv Chem Ser 81. Washington, DC American Chemical Society, 1968 222-230. 

Chen X, Schuler RH. (1993) Directing effects of phenyl substitution in the reaction of hydroxyl radical with aromatics The radiolytic hydroxylation of biphenyl. J Phys Chem 97 421-425. 

Gierer [3] has reviewed the reactions of the hydroxyl radical with lignin. It attacks both the lignin side chains and the aromatic rings, but the ionized form (O") is less reactive and at pHs above the pK, (11.9) only side chain cleavage was observed. 

Pulse Radiolysis Studies. XIII. Rate Constants for the Reaction of Hydroxyl Radicals with Aromatic Compounds in Aqueous Solutions... 

Absolute rate constants have been determined for the reaction of the hydroxyl radical with a variety of aromatic compounds in aqueous solution. The rate constants obtained are significantly higher than values previously reported. Rate constants for the reaction of the hydroxyl radical with methyl alcohol and ethyl alcohol have also been determined by competition kinetics using three of these absolute rate constants as reference values. Comparison of our results with the published values from competition kinetics suggests that the rate constants for the reaction of hydroxyl radicals with iodide ion and thiocyanate ion are significantly higher than reported in earlier work. The ultraviolet absorption bands of the various substituted hydroxycyclohexadienyl radicals formed have been observed. 

Table I. Absolute Rate Constants for the Reactions of Hydroxyl Radical with Aromatic Compounds...

Figure 6.24 Arrhenius plots of log k versus 1000/T for the reaction of hydroxyl radical with toluene and 1,2,3-trimethylhenzene illustrating the response associated with the mechanisms of hydrogen abstraction and addition to the aromatic ring. [Reproduced with permission from R. A. Perry, R. Atkinson, and J. N. Pitts, J. Phys. Chem. 81, 296 (1977). Copyright 1977, American Chemical Society.]...

The nature of the reactions of hydroxyl radicals with polynuclear aromatic hydrocarbons is illustrated by studies of products observed with naphthalene (Fig. 6.25)." Addition of the hydroxyl radical to the aromatic ring produces ring opening with the... 

The Arrhenius parameters of the reactions of hydroxyl radicals with aromatic compounds, listed in Table 2, are based on the rate coefficients (cm molecules" s ) of the reference compounds taken from recent evaluations of OH radical reactions / (2,3-dimethylbutane) = 6.2 x 10" [1], independent of temperature / (diethyl ether) = 7.3 x 10" exp(158K/T), 242-440 K [3] ... 

The aromatic core or framework of many aromatic compounds is relatively resistant to alkylperoxy radicals and inert under the usual autoxidation conditions (2). Consequentiy, even somewhat exotic aromatic acids are resistant to further oxidation this makes it possible to consider alkylaromatic LPO as a selective means of producing fine chemicals (206). Such products may include multifimctional aromatic acids, acids with fused rings, acids with rings linked by carbon—carbon bonds, or through ether, carbonyl, or other linkages (279—287). The products may even be phenoUc if the phenoUc hydroxyl is first esterified (288,289). 

A chlorohydrin has been defined (1) as a compound containing both chloio and hydroxyl radicals, and chlorohydrins have been described as compounds having the chloro and the hydroxyl groups on adjacent carbon atoms (2). Common usage of the term appHes to aUphatic compounds and does not include aromatic compounds. Chlorohydrins are most easily prepared by the reaction of an alkene with chlorine and water, though other methods of preparation ate possible. The principal use of chlorohydrins has been as intermediates in the production of various oxitane compounds through dehydrochlorination. 

The transformation of arenes in the troposphere has been discussed in detail (Arey 1998). Their destruction can be mediated by reaction with hydroxyl radicals, and from naphthalene a wide range of compounds is produced, including 1- and 2-naphthols, 2-formylcinnamaldehyde, phthalic anhydride, and with less certainty 1,4-naphthoquinone and 2,3-epoxynaphthoquinone. Both 1- and 2-nitronaphthalene were formed through the intervention of NO2 (Bunce et al. 1997). Attention has also been directed to the composition of secondary organic aerosols from the photooxidation of monocyclic aromatic hydrocarbons in the presence of NO (Eorstner et al. 1997) the main products from a range of alkylated aromatics were 2,5-furandione and the 3-methyl and 3-ethyl congeners. 

Endogenous or exogenous aromatic compounds such as phenols and phenolic acids react extremely rapidly with OH radicals to form a mixture of hydroxylated products (Halliwell et /., 1988). Indeed, aromatic hydroxylation serves as an efiective method for evaluating OH radical activity both in vitro (Moorhouse et al., 1985 Grootveld and Halliwell, 1986a) and in vivo (Grootveld and Halliwell, 1986b). 

If an aromatic compound reacts with an OH radical to form a specific set of hydroxylated products that can be accurately identified and quantified in biological samples, and one or more of these products are not identical to naturally occurring hydroxylated species, i.e. not produced by normal metabolic processes, then the identification of these unnatural products can be used to monitor OH radical activity therein. This is likely to be the case if the aromatic detector molecule is present at the sites of OH radical generation at concentrations sufficient to compete with any other molecules that might scavenge OH radical. 

Several studies have been performed on the photodecomposition of diaryl sulfones and polysulfones Khodair, et. al., (21) demonstrated that the photodecomposition of diaryl sulfones proceeds by a free-radical mechanism with initial carbon-sulfur bond cleavage. This gives an aryl radical and an aromatic sulfonyl radical. The latter radical can react with oxygen and a hydrogen donor to eventually form the hydroxyl radical. The hydroxy radical may attack the aromatic nucleus in PET and forms the hydroxyterephthaloyl radical. 

---