STUDIES IN OZONOLYSIS. I. ACTION OF OZONE ON SOLVENTS USED IN OZONIZATION¹

Abstract

From the very beginning (1) of the study of ozonolysis it has been rather well recognized that the solvents commonly used for this reaction are attacked more or less by ozone. The literature contains many qualitative and contradictory statements regarding the action of ozone on numerous solvents. In only one case (2) could any quantitative information be found. Some investigations (3, 4, 5,6) have been reported, in which a quantitative determination of the ozone decomposed by the solvent must have been carried out, but no pertinent data were given.

Ozonolysis of Canola Oil: A Study of Product Yields and Ozonolysis Kinetics in Different Solvent Systems

“…This result can be explained as follows: the presence of ethyl acetate (in which canola oil and ozonolysis products are soluble) leads to efficient ozonolysis due to the miscibility of canola oil in this solvent. At the same time, the presence of alcohol prevents the formation of unwanted carboxylic acids by trapping zwitterions in alcohols [40] thus forming esters and/or by absorbing ozone [39] as discussed above. However, a further increase of the ozonolysis time (60 min and more) leads to a dramatic increase in the formation of carboxylic acids.…”

“…A further increase in the ozonolysis time beyond this point did lead to the formation of small amount of carboxylic acids in both systems, but the amount of acid formed was still significantly lower than in the system where ethyl acetate was used as the solvent. Since it is known that the alcohols are very reactive towards ozone [39], the observed decrease in the oxidation of aldehydes to carboxylic acids in the presence of alcohols is most is likely due to the preferential oxidation of those alcohols by ozone over the oxidation of aldehydes. Hence, when using methanol or ethanol as the solvent, the formation of formic and acetic acid dominate over the formation of carboxylic acids from oxidation of the light ozonolysis products.…”

“…The formation of oligomeric compounds was negligible using both alcohols as solvents. It has long been known that methanol and ethanol are the most reactive solvents toward ozonolysis [39]. Furthermore, it has been shown that if ozonolysis of an alkene is carried out in excess alcohol, the zwitterion intermediate can be trapped in the form of an alkoxy-hydroperoxide [40] or a peroxy hemi-acetal (Scheme 1I).…”

The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system – a review

“…In light of this, the following solvent effects should be noted: -Product distributions (i.e. the types and/or relative yields of products) in solutions that are treated by ozonolysis often depend on the solvent (Bailey, 1958(Bailey, , 1978Greenwood, 1945;Pryde et al, 1968) -The presence and types of peroxidic products appears especially sensitive to the type of solvent (Bailey et al, 1974;Fliszár et al, 1966;Murray, 1968;Zelikman et al, 1971;Bailey, 1958;Bernatek et al, 1967) -Treatment of ozone-reacted mediums with acids (Bernatek et al, 1967;Bernatek and Ledaal, 1960;Bailey, 1978) may decompose ozonides and cause the formation of peroxyacids along with carbonyls. It is also well-established that bases can decompose ozonides and other peroxidic products of ozonolysis, forming ketones or aldehydes and carboxylic acids (Bailey, 1978).…”

Tetracyclic triterpenes. X. Solvent effect in reactions of tetrasubstituted triterpenoidal olefins with ozone. An allylic oxidation

“…Thin-layer chromatographic monitoring of the reaction showed that the epoxy-ketone 7 was the primary product of the reaction. Dehydration of 7 to the diene 5 was catalyzed by an acid4 formed from the solvent under ozonolysis conditions (7). This was evidenced by the isolation of the epoxy-ketone 7 (5 1 % yield) and the enone 9 (5%) from the reaction of 4 carried out in the same solvent containing a small amount of pyridine (8).…”