Reactions of Free Radicals with Aromatics. I. The Unimportance of the “Identity Reaction” with Benzylic Radicals¹

The Magnitude of the Primary Kinetic Isotope Effect for Compounds of Hydrogen and Deuterium.

“…The ratio for the oxidation by permanganate of benzaldehyde in neutral aqueous solution (45) is 7, for the oxidation by permanganate of formate ion (48) is 7.4, and for the oxidation of desoxybenzoin by selenious acid ( 12) is about 6; the chromic acid oxidation of phenyl-feributylcarbinol in 86.5 per cent aqueous acetic acid gives a kinetic isotope effect (20) for deuterium of 14, and the permanganate oxidation of phenyltrifluoromethylcarbinol (40) in alkali one of 16. The attack of methyl radicals from diacetyl peroxide on toluene shows an isotope effect (15), measured from the methane produced, of nearly 9. The reaction of the lithium salt of cyclohexylamine with -deuteroethylbenzene shows an 1 No distinction is here intended between H+, H•, and H~; the term "hydrogen atom" is used for all.…”

New Metal Salt-Induced Homolytic Reactions. II. Modification of Free Radical Reactions by Copper Salts1

“…C6HS(CH3)2C• + Cu+ ^C'cHi(CH3)2C-Cu+(21) i v i d u a l n o t d i r e c t l y a s s o c i a t e d w i t h s c i t e i s p r o h i b i t e d . C,H6(CH3)2C-Cu+ + (CeHiCOOs -> C6H6(CH3)2C02CC6H6 + C6H6C02• + Cu+ (22) C6H6(CH3)2C• + Cu++->-Cumyl alcohol and acetophenone(23) …”