KINETICS AND MECHANISM OF ADDITION OF ACIDS TO OLEFINS .4. ADDITION OF HYDROGEN AND DEUTERIUM CHLORIDE TO 3-METHYL-1-BUTENE, 3,3-DIMETHYL-1-BUTENE, 1-METHYLCYCLOPENTENE, AND 1-METHYLCYCLOPENTENE-2,5,5-D3

The addition of hydrogen and deuterium chloride to 3-methyl-l-butene, 3,3-dimethyl-1-butene, 1-methylcyclopentene, and 1 -methylcyclopentene-2,5,5-d3 has been studied in nitromethane at 25.0°. In the initial stages of the reaction, 3-methyl-1-butene is shown to form 40% normal addition product, 2-chloro-3-methylbutane, and 60% rearranged product, 2-chloro-2-methylbutane, while 3,3-dimethyl-1-butene is shown to form only 17% normal addition product, 2-chloro-3,3-dimethylbutane, and 83% rearranged product, 2-chloro-2,3-dimethylbutane. Hydrogen chloride catalyzes the rearrangement of 2-chloro-3-methylbutane but control experiments show that the rate of this Wagner-Meerwein rearrangement is too slow to account for the observed product ratio during the initial stages of the addition reaction. Under similar conditions the rearrangement of 2-chloro-3,3-dimethyl-butane is very slow and can be neglected. The addition of deuterium chloride to 1-methylcyclopentene and of hydrogen chloride to 1 methylcyclopentene-3,5,5-d3 is shown to lead to 96 ± 4% trans-addition product. © 1969, American Chemical Society. All rights reserved.