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- W2951549172 abstract "The peroxyacyl nitrates 1b and 1c, in cyclohexane solution (0.01 − 0.1 M, 25-60°C) decompose smoothly, displaying first-order kinetics. Added nitrogen dioxide lowers the rate (approx. 3 x) but added nitric oxide results in a (7-fold) rate enhancement, independent of the NO concentration. Under the latter circumstances the Arrhenius parameters for 1b are: log A/s−1 = 15.3, Ea = 26.7 kcal.mole−1.Products from 1b include CO2 (>85%), RNO2, RONO, ROH and corresponding derivatives from solvent cyclohexane. 1b does not produce caproic acid, but m-chlorobenzoic acid together with chlorobenzene (RH), are prominent products from the thermolysis of 1c.These features are interpreted via a homolytic mechanism involving primary steps [1] and [2]. With added NO, step [1] is rate-determining, whereas with added NO2 decomposition occurs via reaction [2].The relevance of radical pair (cage) processes is outlined.Attack on solvent occurs by transient free-radical intermediates (e.g. R*, RO*) and by nitrogen dioxide.The effect of other additives (such as dihydroanthracene, resulting in RCO3H as isolable product) is in accord with this mechanism.Thermochemical-kinetic features are discussed." @default.
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- W2951549172 date "1978-07-11" @default.
- W2951549172 modified "2023-09-28" @default.
- W2951549172 title "ChemInform Abstract: CHEMISTRY OF PEROXYACYL NITRATES I. THERMAL DECOMPOSITION IN CYCLOHEXANE SOLUTION, EFFECT OF ADDED NITRIC OXIDE AND OF NITROGEN DIOXIDE" @default.
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