Reactions of ozonides. VII. Isolation and oxidation of ozonolysis products from 1-decene

Abstract

1-Decene ozonide (1) was isolated by column chromatography of the mixed products of ozonation of 1-decene (2) in several nonpolar solvents. 1-Methoxy- (3) and 1-tertiary butoxynonane-1-hydroperoxide (4) were similarly obtained. The thin-layer chromatographic separation of these products from each other and from other ozonation products was examined. Compounds 3 and 4 were smoothly oxidized to di-(1-alkoxyalkyl)peroxides by Ce(IV). The stoichiometry of this reaction, examined by isothermal calorimetry, was 1:1. Compounds 1,3, and 4 were oxidized by CF3CO3H and by other oxidizing agents to nonanoic acid with chain degradation loss of 2–30%.

Radiation‐induced oxidation of solid poly(ethylene oxide). II. Mechanism

“…From our experimental results, it can be inferred that the oxidative degradation of PEO proceeds mainly through a chain process via the sequence of reactions (l), (4), (7), (8), (ll), and (12) (marked by boldface arrows on the scheme in Fig. 1) which leads to the observed large G values for the production of chain scissions, formate, and hemiformal groups.…”

“…The principal fate of the secondary alkoxy radicals evolved in reaction (4) is the hydrogen abstraction from the polymer to give hemiacetal groups [reaction (511 or the decomposition by /3 scission with formation of an aldehyde [reaction (6)] or formate [reaction (7)] terminal group, depending on which bond has been broken. The observed high yields in formate groups and low yields in aldehyde groups indicate that reaction (7) is much favored over reaction (6), in agreement with Kulevsky'sll results on the oxidation of diethyl ether. The products of /3 scission of the alkoxy radical could also be formed in a step concerted with 0-0 homolysis of the tetroxide resulting from P02.…”

“…Reactions of Primary PO20 and PO* Radicals. The primary a-alkoxyalkyl radical generated in reaction (7) is expected to be sufficiently stable at ambient temperature to react mostly with the gaseous oxygen with formation of a primary peroxy radical12 [reaction (8)]. This P02-radical is then assumed to disappear either by hydrogen abstraction from the polymer [reaction (9)], either by terminating [reaction (lo)] or nonterminating [reaction (ll)] interactions with another primary or secondary peroxy radical.…”

“…In order to account for carbon dioxide production, we assume that a significant fraction of the a-alkoxymethyl radicals evolved in reaction (7) can abstract the labile hydrogen atom of the formate group formed simultaneously and generate a-alkoxyacyl radicals ROC=O [reaction (15)]. 16 These radicals have been shown17 to be unstable, even a t room temperature, and to yield exclusively alkyl radicals and carbon dioxide [reaction (16)].…”

Reactions of Ozonides. IX. A Radioisotopic Dilution Study of Ozonide Methanolysis

“…In order to facilitate additional purification of the isolated methoxyhydroperoxide it was converted to a diperoxide using ceric ammonium nitrate (8). The diperoxide was subjected to fractionation on an Eastman Chromagram sheet and the major regions of the chromatogram were examined for radioactivity.…”