Ozonolysis mechanistic studies

The most complete mechanistic studies have been made with trisubstituted silanes, which initially undergo an exclusive silicon-hydrogen bond cleavage. Retention of configuration occurs in the ozonolysis of 1-decahydronaphthylcyclohexylmethylsilane 68 to the corresponding hydroxide ... 

Thomas, W., Zabel, F., Becker, K. H., and Fink, E. H. (1995) A mechanistic study on the ozonolysis of ethene, in Tropospheric Oxidation Mechanisms, edited by K. H. Becker. European Commission. Report EUR 16171 EN, Luxembourg, pp. 315-320. 

The ozonolysis reaction has been the subject of considerable mechanistic study. It is likely that in most cases the reaction proceeds by breakdown of the 1,3-dipolar cycloaddition product to a carbonyl oxide 99 and an aldehyde (or ketone) (5.99). The fate of the carbonyl oxide depends on the solvent and on its structure and the structure of the carbonyl compound. In an inert (non-participating) solvent, the carbonyl compound may react with the carbonyl oxide to form an ozonide 100 otherwise the carbonyl oxide may dimerize to the peroxide 101 or give ill-defined polymers. In nucleophilic solvents such as methanol or acetic acid, hydroperoxides of the type 102 are formed. 

Spectroscopic, kinetic, photolytic and mechanistic studies have been carried out on simple peroxy radicals such as HO2, CH3O2, C2H5O2 and CH3C(0)02 using a variety of laboratory techniques. The photo-oxidation studies of selected carbonyl compounds was performed and quantum yields established in order to assess their photolytic lifetime in the troposphere. The product distribution of the ozonolysis of selected alkenes was determined in the presence of water vapour. 

Kinetic and mechanistic studies of the ozonolysis of alkenes under atmospheric conditions,... 

T he ozonolysis of pure hydrocarbon olefins has been studied by gen-erations of chemists ever since 1905 when Harries established the interaction of ozone with double bonds. During this continued research practically all aspects of the ozonolysis reaction have been extensively scrutinized, starting from the nature and products of the initial ozone-double bond interaction, via the mechanistic and stereochemical course of the ozone cleavage, to the correlation between the nature of the starting material and the reaction products. Consequently, the ozonolysis of hydrocarbon olefins is rather well understood. 

The reaction of olefins with ozone constitutes an important method of cleavage of carbon-carbon double bonds. This reaction has been a degradative tool for several decades and finds occasional use in synthesis. Recent years have seen the application of low-temperature and spectroscopic techniques to the study of the rather unstable species that are intermediates in the ozonolysis process. These studies have put early mechanistic ideas on a firmer basis and have elaborated many additional details of the reaction mechanism. 

In Summary Ozonolysis followed by reduction yields aldehydes and ketones. Mechanistically, the reactions presented in Sections 12-10 through 12-12 are related in as much as the attack of an electrophilic oxidizing agent leads to rupture of the tt bond. Unlike the reaction sequences studied in Sections 12-10 and 12-11, however, ozonolysis causes cleavage of both the TT and the cr bonds. 

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