Reactions of Atoms and Free Radicals in Solution. Xxvii. The Decomposition of Diacetyl Peroxide in Alcohols

Studies in chain transfer IV. Catalyzed polymerization of vinyl acetate

“…In agreement with our previous observation and the active a-hydrogen theory, the four butyl alcohols are active in the order secondary > normal, iso > tertiary. Our surmise that hydroxylic hydrogen does not take any part in free radical attack has lately received striking confirmation by the results obtained by Kharasch, Rowe & Urry (1951) by subjecting deuterobutyl alcohol, C4H9OD, to free radical attack.…”

“…This conclusion is confirmed by the work of Kharasch, McBay & Urry (1945), who have shown th a t the free radicals from decomposing acetyl peroxide remove the a-hydrogen atom from ethyl benzene and isopropyl benzene, leaving the substituted benzyl residues to dimerize. The acidities of hydrocarbons determined by Conant & Wheland (1932) and McEwen (1936) are in the same order as the transfer constants, which probably indicate that the more a CH bond is polarized owing to inductive or tautomeric drainage of electrons by the group attached to the carbon, the more susceptible it is to an attack by a free radical.…”

Radical Substitution In Aromatic Nuclei

“…In one case the generating radicals came from benzoyl peroxide and the alkoxyl radicals from isobutyl alcohol; o-and p-isobutoxybenzoic acids mere produced (157). Some doubt of the accuracy of this observation has been expressed, since no alkoxyl radicals are formed from diacetyl peroxide and alcohols (261). Kevertheless, autoxidizing tetralin in ethanol converted benzoic acid to ethoxybenzoic acids (I 48).…”

Free radicals: XXVIII. Reaction of 2,4,6-triphenylpyranyl with (diacetoxy-λ3-iodanyl)benzene

“…Excess compound II over I after attainment of their equimolar ratio does not affect the amount and composition of the gaseous products (methane and carbon dioxide). ** However, the amount of pentenedione V which could be formed only from pyranyl I [8][9][10] decreases as the reactant ratio increases and remains constant when the reactant ratio becomes equimolar (Fig. 1).…”

“…We also examined the reaction of pyranyl radical I with compound II at a reactant ratio of 0.67 : 1 (mmol/mmol) at different temperatures with a view to ** These compounds are formed as the major products in thermal decomposition of acetyl peroxide in isopropyl alcohol [9]. estimate temperature effect on the product composition (Fig.…”