Solvolytic Behavior of Ο- (1-Cyclopropylethyl) S-Methyl Dithiocarbonate and Related Compounds

Abstract

Ο- (1-Cyclopropylethyl) S-methyl dithiocarbonate (Ib) was solvolyzed in various solvents to give S- (1-cyclopropylethyl) S-methyl dithiocarbonate (IIb) quantitatively. The reaction obeyed the first-order rate law and the rates were considerably affected by the polarity of the solvent used. Phenolysis of Ib with p-chlorophenol gave IIb and a small amount of the phenol ether. Plots of the logarithm of the reaction rates against Y values gave a linear relationship. The reaction was found to be markedly accelerated by phenolic solvents. The rate in p-chlorophenol is 509 times faster than that in ethanol. The role of hydrogen-bonding to the thione sulfur in the rearrangement reaction is discussed.