A review of the literature concerning reactions of ozone with amines has given rise to the working hypothesis that these reactions all involve initially the electrophilic attack of ozone to give an adduct for which at least three different reaction routes are available: loss of molecular oxygen to give an amine oxide or further reaction products thereof, an intramolecular oxidation of a side chain, and dissociation to nitrogen cation radicals and the ozonate anion radical, followed by further reactions of these. Results from ozonations of tert-butylamine and tri-n-butylamine, which furnish additional evidence for the above competitions, are described.>Tphe literature suggests several ways in which ozone reacts with amines.
Faust spinning-band column to yield 151 g of analytically pure product (Table I).Rate Measurements.-Gas chromatographic analyses were performed using a Beckman GC-2A gas chromatograph, equipped with a 10-in. recorder and Disc integrator, and containing a 2 ft x 0.25 in. column of 30YG silicone 550 on 42-60 mesh firebrick.Concentrations were obtained as a function of time by comparing the integrated area of a reactant peak a t time t with the area of that peak at time to. Since the to peak corresponded to a known initial concentration, the actual concentration a t time t was found from the ratio of peak areas.I n a typical run, 2.00 x 10-4 mol of glycidyl ether and 2.00 x 10-4 mol of dibutylamine were weighed into a 10-ml volumetric flask, and enough t-amyl alcohol was added to bring the total volume to exactly 10 ml.16r1' The solution was then immediately transferred to a round-bottom flask equipped with a magnetic stirrer and a self-sealing rubber septum cap. The flask was capped and placed in a constant temperature bath, which was maintained a t the reaction temperature 3~0 . 0 5~. The to reading was then taken by piercing the septum cap with a syringe and withdrawing a 10.0-pl aliquot, which was injected directly into the gas chromatograph for analysis. Subsequent 10 .O-p1 samples were withdrawn a t various times and analyzed in an identical manner. Variation in the height of the sharp t-amyl alcohol peak, which served as an internal standard, was generally less than lYG during a run, and never more than 2.5YG. All reactions were followed to a t least 60% completion.Each of the reactions was run at, three different temperatures (41.0, 51.0, and 60.0") using initial concentrations of 0.200 M in t-amyl alcohol for each reactant. All of the 60" reactions were run in duplicate. Rate constants were reproducible to within 1% in most cases, and to within 370 in the least favorable case. Product Analysis.-Product investigation was done by glpc analysis of the infinite-time kinetic samples. A 6 f t X 0.25 in.
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