Kinetic investigation of the hydrochlorination of olefins in aprotic solvents and sulfonation of idobenzene and the selectivity relation

• Main Author: Davies, Thomas Glen
• Format: Others
• Published: BYU ScholarsArchive 1962
• Subjects: Chemistry; Organic; Sulfonation; Alkenes; Benzene
• Online Access: https://scholarsarchive.byu.edu/etd/8196; https://scholarsarchive.byu.edu/cgi/viewcontent.cgi?article=9196&context=etd

Kinetic investigation of the hydrochlorination of cyclohexene and cis-2-butene in n-heptane with SnCl4 as catalyst shows that the reaction is second order with respect to both olefin and catalyst. The specific rate constants at 25° , 0° and -23.8°C and the activation parameters were determined. Investigation of the Ga2Cl6 catalyzed hydrochlorination of cyclohexene and cis-2-butene in dichloromethane indicates that alkylation and polymerization compete with the hydrochlorination reaction in the presence of the solvent. The relative reaction rates and the isomer distribution for the sulfonation of iodobenzene by S35O3 have been determined in refluxing SO2 at -10°C. The reaction resulted in 98.4 ± 1.1 % para, 1.1 ± 1.0% meta and 0.8 ± 0.5% ortho substitution. The partial rate factors determined were Pf 2.2, Mf 0.013, Of 0.009. The relative rate ratios k(C6H5CH3/C6H5I) and k(C6H5I/C6H6) were 29.0 ± 7.2 and 0.37 ± 0.10, respectively. The high para partial rate factor indicates that a significant difference exists between the Brown-Hammett selectivity relation and experimental determination.