pH Effects on Ethanolysis of Some Arenediazonium Ions: Evidence for Homolytic Dediazoniation Proceeding through Formation of Transient Diazo Ethers

• Published in: European journal of organic chemistry 2004-08, Vol.2004 (15), p.3221-3226
• Main Authors: Pazo-Llorente, Roman, Bravo-Diaz, Carlos, Gonzalez-Romero, Elisa
• Format: Article
• Language: English
• Subjects: Alcohols; Arenediazonium ions; Dediazoniation; Kinetics; Solvolysis
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.200400170

The effects of pH on the observed rate constants (kobsd.) and on the solvolytic dediazoniation product distributions of ethanolysis of 2‐, 3‐, and 4‐methylbenzenediazonium ions (2MBD, 3MBD, and 4MBD, respectively) were determined by a combination of spectrophotometric (UV/Vis) and chromatographic (HPLC) techniques. The variation of both kobsd. and product yields with pH follow S‐shaped curves with inflection points at pH ≈︁ 3.6, depending on solvent composition. With increasing pH, kobsd. values increase by factors of up to about 4 (2MBD), about 3 (3MBD), and about 50 (4MBD) with respect to the kobsd. values at low pH. HPLC analyses of the reaction mixtures show that only heterolytic products are obtained at low pH, indicating that solvolytic dediazoniation takes place through an ionic mechanism, but an increase in pH favors homolytic dediazoniation, with quantitative conversion into the reduction product toluene being obtained at pH ⩾ 6 (4MBD), indicating that a turnover from the heterolytic to the homolytic mechanisms is taking place under experimental conditions under which insignificant amounts of EtO− or OH− should be present in solution. The obtained S‐shaped profiles suggest that the initiation process of the homolytic pathway is the result of the formation of a highly unstable transient diazo ether complex and not by direct electron transfer from the solvent (EtOH) to the arenediazonium ions as is currently believed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)