Polystyrene, ozonolysis

Intramolecular Dieckmann cyclization of polystyrene-bound pimelates has been used to prepare (l-keto esters (Entry 4, Table 3.41). Oxidative cleavage reactions leading to the formation of aldehydes include the ozonolysis of resin-bound alkenes, the periodate-mediated cleavage of 1,2-diols, and the oxidation of Wang resin derived ethers (Entries 5-7, Table 3.41). 

Substrates suitable for oxidative conversion into carbonyl compounds are alkenes, primary or secondary alcohols, and benzyl halides. Polystyrene-bound alkenes have been converted into aldehydes (with the loss of one carbon atom) by ozonolysis followed by reductive cleavage of the intermediate ozonide (Entry 1, Table 12.3). 

It was found that when grafting methyl methacrylate or styrene to rubber, the branches of polymethyl methacrylate or polystyrene are much smaller than was expected, while almost 50 per cent more vinyl polymer was bound than predicted (8, 27, 129, 130, 160, 161). The length of the side branches was determined after oxidation of the rubber, usually by ozonolysis (28, 71, 131) or by perbenzoic acid oxidation followed by periodate treatment (168). 

Saito et al. [107] investigated ozonolysis of polystyrene in carbon tetrachloride. Their results indicated the formation of carboxylic acids and,... 

This will ultimately result in decrease of the rate constant. Table 10.2 shows some examples of ozonolysis of saturated polymers—polystyrene and polyisobutylene. These reactions take place not through the mechanism of ozone reaction with the double bonds but through a hidden radical mechanism with rate constants of four to five orders of magnitude lower. 

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