Rate and Product Studies of Solvolyses of Benzyl Fluoroformate

• Main Authors: Dennis N. Kevill, Seung Han Ryu, Jin Burm Kyong
• Format: Article
• Language: English
• Published: MDPI AG 2006-07-01
• Series: International Journal of Molecular Sciences
• Subjects: benzyl fluoroformate; addition–elimination; solvent isotope effect; Grunwald– Winstein equation; product selectivity.
• Online Access: http://www.mdpi.com/1422-0067/7/7/186/

The specific rates of solvolysis of benzyl fluoroformate have been measured inseveral hydroxylic solvents at 25.0 °C. For methanolysis, the solvent deuterium isotopeeffect and activation parameters were determined and activation parameters were alsodetermined for solvolyses in ethanol and 80% ethanol. For several of the binary hydroxylicsolvents, measurement of product ratios allowed selectivity values to be determined. Anextended Grunwald–Winstein treatment of the data led to sensitivities to changes in solventnucleophilicity and ionizing power. Comparison with previously determined specific ratesfor solvolysis of the chloroformate gave fluorine/chlorine rate ratios greater than unity. Allof the determinations made were consistent with an addition–elimination (association–dissociation) mechanism, with addition rate-determining.