1,4-Carbonyl participation in solvolysis of alkyl toluene-p-sulphonates

Abstract

2,2-Dimethyl-3-oxo-3-phenylpropyl toluene-p-sulphonate (tosylate) and some related 3-oxoalkyl tosylates are solvolysed in buffered carboxylic acid solvents by 1,4-carbonyl participation to give unrearranged carboxylate esters. The reactions are too fast to be direct displacements, and do not occur in similar compounds which lack the carbonyl group. Secondary alkyl tosylates in the same series also react by 1,4-carbonyl participation but the intermediate cation fragments, as well as reacting with solvent to give unrearranged products.