1979/10/15 by Wilkins Reeve, Charles M. Erikson, Patrick F. Aluotto · 113 citations
Chemical Engineering · Chemistry · #Alcohol #Alkoxide #Analytical Chemistry and Chromatography #Bromide #Catalysis #Chemical and Physical Properties in Aqueous Solutions #Chemistry #Ethanol #Ether #Free Radicals and Antioxidants #Hydrolysis #Hydroxide #Inorganic chemistry #Isopropyl #Isopropyl alcohol #Medicinal chemistry #Methanol #Methoxide #Nucleophile #Organic chemistry #Phenol #Potassium hydroxide #Reactivity (psychology) #Solvolysis
paper · pdf · doi:10.1139/v79-444
published in Canadian Journal of Chemistry 57(20), 2747-2754 (NRC Research Press)
openalex publication_date 1979/10/15 · openalex created_date 2025/10/10 · openalex updated_date 2026/06/11
A new semiquantitative method has been developed for measuring the relative acidities of methanol, ethanol, isopropyl alcohol, and tert-butyl alcohol in mixed hydroxylic solvents. A solution of the alkoxides of two alcohols in an excess of the two alcohols is allowed to react with n-butyl bromide to form a mixture of two ethers. The composition of the ether mixture is a measure of the "competitive reactivity" of thetwo alkoxides. This can be measured directly, and in theory can be factored into two components: the relative nucleophilicity and the relative basicity of the two alkoxides. Relative nucleophilicities are determined by using solutions in which phenol is one component. Knowing the competitive reactivities and nucleophilicities, the relative acidities of methanol, ethanol, isopropyl alcohol, and tert-butyl alcohol in alcoholic media are shown to be 4.4, 1.0, 0.24, and 0.21, respectively. The relative nucleophilicities of hydroxide, methoxide, ethoxide, isopropoxide, tert-butoxide, phenoxide, and m-cresoxide are 0.08, 0.82, 1.0, 0.4, 0.04, 0.46, and 0.57 respectively.