ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

Paramagnetic products formed in the reactions of organometallic compounds. XV. Influence of solvents on diaryl ketyl radicals

E. Maťašová-Kutejová, A. Staško, and Ľ. Malík

Department of Physical Chemistry, Slovak Technical University, 812 37 Bratislava

Abstract:  Ketyl radicals PhCO ^-. —R arise as products of the reactions of benzenecarboxylic acid (PhCOOH) with phenylmagnesium bromides (RMgBr) in the presence of nickel in diethyl ether provided the ratio RMgX: PhCOOH≐4. An addition of solvents, such as Pr2O, n-Bu₂O, tert-BuOMe, benzene, toluene, hexane, cyclohexane to diethyl ether has no influence on the course of reaction and the values of splitting constants of the investigated radicals. The presence of dimethoxyethane, dioxan, and hexamethylphosphortriamide manifests itself by a change in splitting constants and the stability of radicals increases from one to several days. Moreover, a greater excess of RMgBr (RMgBr: PhCOOH≐8) is necessary for generation of the radicals. A new type of intermediates — aroyl radicals may be observed in tetrahydrofuran.

Full paper in Portable Document Format: 364a481.pdf

Chemical Papers 36 (4) 481–487 (1982)