Peroxy butyl nitrate

Attention has been given to possible adverse effects of incorporating tert-butyl methyl ether into antomobile fuels. tert-Butyl formate is an established product of photolysis, and it has been shown that photolysis in the presence of NO can produce the relatively stable tert-butoxyformyl peroxynitrate. This has a stability comparable to that of peroxy-acetyl nitrate, and may therefore increase the potential for disseminating NO (Kirchner et al. 1997). 

For monoalkyl benzenes, there is evidence of a second mechanism for hydrocarbon decomposition. Since substantial amounts of benzalde-hyde (representing a 5-25% yield) and traces (< 1% yield) of peroxy-benzoyl nitrate have been identified (10) in smog chamber experiments with aromatic hydrocarbons having at least two benzylic hydrogens, hydrocarbon oxidation apparently may occur at the a-carbon atom. Application of the usual Hammett treatment and electrophilic substituent constants (23) to any of our rate measurements for toluene, fert-butyl-benzene, and benzene indicates no linear Hammett relationship toluene... 

Dimethy lethyl peroxynitrate, 5ee tert-Butyl peroxy nitrate, 1663... 

Carotenoids, in particular P-carotene, are well-known free-radical quenchers [78]. It has been shown that peroxy radicals can oxidise P-carotene to the corresponding radical cations [78]. Absorption spectra demonstrate the appearance of broad bands in the range 600-1000 nm with = 910 nm (e = 9.4 x lOVM/cm) during pulse radiolysis of solutions of P-carotene in tert-butyl alcohol - water mixtures containing nitrate [79]. These bands were attributed to P-carotene radical cations generated by electron abstraction from the substrate by NO radicals ... 

The 2-butoxy, and 1-butoxy radicals formed in the reactions of 2-butyl and 1-butyl peroxy radicals with NO (path (d) and (j)), react with O2 to produce HO2 together with carbonyl compounds such as methyl ethyl ketone and butanal (path (g) and (1)), and complete the HO cycle. Under the typical NO concentrations in the polluted atmosphere, the formation rate of alkyl nitrates by the reactions of alkoxy radicals with NO2 is negligible, the recombination isomerization reaction by the alkylperoxy radicals with NO is the major pathway as the formation process of alkyl nitrate. 

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