Intramolecular Radical Reactions. Decomposition of o-Methyl-, o-Benzyl-, and o-Phenylbenzoyl Peroxide

Abstract

Decompositions of o-methyl-, o-benzyl-, and o-phenylbenzoyl peroxides have been studied in carbon tetrachloride in the presence and absence of iodine and iodine plus water (Tables I-IV). In carbon tetrachloride alone, for the o-methyl compound the ratio of decarboxylation to intramolecular hydrogen transfer is 2.5 to 1. The radical derived from hydrogen transfer undergoes cross-termination with the trichloromethyl radical and like-termination. In the o-benzyl compound intramolecular

6H-Dibenzo[b,d]pyrans. I. Synthesis

“…In the earlier literature the copper-catalyzed condensation of the diazonium salt of an anthranilic acid and the appropriate phenol (2, 3) or of the corresponding phenyl anthranilate (4, 5) was frequently employed although the yields were generally very low. More recently the oxidative cyclization (6-10) of biphenyl-2-carboxylic acids and the decomposition of the corresponding peroxides (5, 8, [11][12][13][14] have been investigated. The intramolecular.…”

“…Substitution of the benzylic hydroxyl with bromine via 12 13 hydrogen bromide, followed by dehydrohalo-…”

Reactions of carboxylic acid derivatives with superoxide

“…However, this result is misleading since a high conversion (90%) of peroxy acid into acid can be achieved simply by shaking for 15 min a solution of m-chloroperoxybenzoic acid with aqueous potassium superoxide. Hence, the superoxide, which disproportionates according to Equation (6), is simply a source of hydroxide ion which displaces hydroperoxide-anion as indicated in Equation (7).…”

Addition of oxime anions to dienophiles

“…The preparative value of decomposition of benzoyl peroxide in boiling carbon tetrachloride solutions of iodine was reported by Hammond and Soffer who obtained an 85% yield of iodobenzene in 36-48 hr.3 Low yields (15-20%) were observed in benzene and chlorobenzene.4 o-Iodotoluene was similarly obtained in about 49% yield from o-toluoyl peroxide in boiling carbon tetrachloride in 17 hr. 5 The reaction of peroxide with iodine may be more usefully applied by reducing the reaction times at higher temperatures. Accordingly, benzoyl and pelargonyl peroxide, representing aromatic and aliphatic classes, were each decomposed in iodine solutions of higher boiling aromatic and aliphatic solvents to determine the appropriate solvent, optimum conditions, and some of the accompanying side products of the reaction.…”