Peroxy benzoyl nitrate

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... 

General Motors has reported that benzaldehyde, the major aromatic aldehyde in exhaust gas, is a necessary intermediate in photochemical reactions leading to the formation of peroxy-benzoyl nitrate (PBzN) (15). A major portion of eye irritation... 

UV irradiation of the exhaust hydrocarbon-NOx mixture increases the formation of formaldehyde, PAN (peroxyacetyl nitrate), PBzN (peroxy-benzoyl nitrate), NO2, and ozone. These compounds are of toxicological interest and are important in smog formation. The presence or absence of Et4Pb in gasoline does not affect the photochemical reactivity of the exhaust hydrocarbons produced from gasoline (Heuss et al, 1974). 

Oxidation of sulfides to sulfoxides. This well-known nitrating agent has been found to be a suitable reagent for oxidation of sulfides to sulfoxides without frirther oxidation to sulfones. The reaction is carried out at 0° yields are generally in the range of 80-1007<>. Surprisingly the reaction is faster than that with peroxy compounds. In the case of sulfoxides that tend to give Pummerer-type reactions with ACaO, benzoyl nitrate is the preferred oxidant. This acyl nitrate is prepared from benzoyl chloride and silver nitrate it is somewhat more reactive than acetyl nitrate, and oxidations can be conducted even at —76°. 

Perhydroxyl radical, 75 thermal generation from PNA of, 75 Peroxy radical generation, 75 Peroxide crystal photoinitiated reactions, 310 acetyl benzoyl peroxide (ABP), 311 radical pairs in, 311, 313 stress generated in, 313 diundecanyl peroxide (UP), 313 derivatives of, 317 EPR reaction scheme for, 313 IR reaction scheme for, 316 zero field splitting of, 313 Peorxyacetyl nitrate (PAN), 71, 96 CH3C(0)00 radical from, 96 ethane oxidation formation of, 96 IR spectroscopy detection of, 71, 96 perhydroxyl radical formation of, 96 synthesis of, 97 Peroxyalkyl nitrates, 83 IR absorption spectra of, 83 preparation of, 85 Peroxymethyl reactions, 82 Photochemical mechanisms in crystals, 283 atomic trajectories in, 283 Beer s law and, 294 bimolecular processes in, 291 concepts of, 283... 

Reaction of benzoyl peroxy with NO2 generates peroxybenzoyl nitrate, a PAN type species. At 298 K, the equilibrium constant for formation of the nitrate is 5 x 10 cm molecule" so that, for [NOg] = 2.5 x 10 moleculecm (10 ppb), the equilibrium ratio of the nitrate to the peroxy radical is 10" and the equilibrium is established in less than 1 s. The nitrate reacts with OH, with a rate constant of 1 x 10 cm ... 

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