The sulfonation of toluene at -12.5° C. with sulfur trioxide in liquid sulfur dioxide was found to give 10.03 ± 0.20 % ortho, 0.73 ± 0.20 % meta and 89.24 ± 0.20 % para isomers. This isomer distribution was determined by isotope dilution analysis using sulfur-35 enriched sulfur trioxide. After dilution of aliquots of the neutralized sulfonation mixture with pure sodium salts of each of the isomers prepared from the corresponding toluidines, the isomers were converted to the p-toluidine salts, purified by recrystallization, and counted by liquid scintillation counting. The relative rate of sulfonation of toluene compared to benzene was studied under the same conditions. The analysis in this case was accomplished by ultraviolet spectrophotometry. The only assumption made was that the isomer distribution of toluene does not change when benzene is added during the sulfonation. The results show that the relative rate (kt/kb) is 10.9 ± 1,5 at low benzene to toluene ratios but increases considerably at high ratios. The hydrochlorination of cyclohexerte, cis-2-butene and trans-2-butene with stannic chloride catalyst was studied in n-heptane solvent. The kinetics were found to be considerably influenced by trace impurities, especially moisture. The kinetics were found to be first order in olefin and stannic chloride and from zero to three and one-half order in hydrogen chloride depending on the amount of moisture present. When moisture is absent, unexplained abnormal kinetics occurred. Polymerization, cyclization, alkylation, and dehydrochlorination were insignificant under the conditions of the kinetic experiments.
College and Department
Chemistry and Biochemistry
BYU ScholarsArchive Citation
Guillot, David George, "Refinements in the isomer distribution and relative rate of sulfonation of toluene and hydrochlorination of olefins with stannic chloride catalyst" (1966). Theses and Dissertations. 8216.
Isomerism, Chemistry, Physical and theoretical, Sulfonation, Toluene, Alkenes