The induced decomposition of t-butyl peroxide in solution. Part I. Benzyl methyl ethers as solvents

Abstract

Decomposition of t-butyl peroxide in the benzyl methyl ethers ArCH₂·OMe (Ar = Ph, p-CIC₆H₄, m-CIC₆H₄, p-NO₂·C₆H₄, 3,4-Cl₂C₆H₃, p-PhC₆H₄, p-MeO·C₆H₄, and p-Bu^tC₆H₄) at 110° gave, besides small quantities (3–13%, except for 3,4-Cl₂C₆H₃) of the aldehyde ArCHO and varying amounts of the dimer (Ar[graphic omitted]HOMe)₂, the acetals ArCH(OMe)(OBu^t) in yields of 2·8, 36, 17, 85, 62, 0, 0, and 8·5% respectively. The acetal is considered to be formed through an S_H2 attack by the ether radical ArĊH·OMe on the peroxidic O–O bond rather than coupling between the ether and t-butoxy-radicals, and evidence is presented to support this contention. From the acetal-to-dimer ratios found for the substituted ethers, namely, 0.07, 1.2, 0.5, ∞, ∞, 0, 0, and 0.2 respectively, it is concluded that the reaction is facilitated by increased electrophilicity in the ether radical.