The Action of Chlorosulfonic Acid and of Fluosulfonic Acids on Hydrocarbons
Abstract
A loss in rotation, isomerization, and isotopic exchange were observed when D2SO4 and (+) 3-methylhexane were agitated at 60 deg C; the rate constants of the 3 reactions were almost identical. A mechanism is proposed which involves chain initiation by oxidation of the alkane to a tertiary carbonium ion and chain propagation by hydride ion transfer from the tertiary postion of an alkane to a carbonium ion; the carbonium ion is assumed to attain equilibrium with respect to simple Me shift and isotope exchange before the occurrenece of hydride ion transfer. The rate constant for rotation loss was greater than the constants for isomerization and isotopic exchange with HSO3Cl and HSO3F at -33 deg and -78 deg C; the ratio of rotation/isomerization loss increased with improved stirring. The behavior with halosulfonic acids was attributed to a propgressively higher rate constant for hydride ion transfer than for isomerization and isotopic exchange with decreasing temperature. Commercial HSO3Cl gave rates about 10 times as large as those with pure synthetic HSO3Cl; HCl contamination increased the rates, Cl inhibited reaction, and SOCl2 and SO3 had no effect.
Document Details
- Document Type
- Technical Report
- Publication Date
- Jun 01, 1953
- Accession Number
- AD0014973
Entities
People
- Lucien G. Maury
- Robert B. Scott
- Robert L. Burwell Jr.
Organizations
- Northwestern University