Flash photolytic generation and study of p-quinone methide in aqueous solution. An estimate of rate and equilibrium constants for heterolysis of the carbon-bromine bond in p-hydroxybenzyl bromide.
Flash photolysis of p-hydroxybenzyl acetate in aqueous perchloric acid solution and formic acid, acetic acid, biphosphate ion, and tris(hydroxymethyl)methylammonium ion buffers produced p-quinone methide as a short-lived species that underwent hydration to p-hydroxybenzyl alcohol in hydronium ion catalyzed (k(H(+)) = 5.28 x 10(4) M(-1) s(-1)) and uncatalyzed (k(uc) = 3.33 s(-1)) processes. The inverse nature of the solvent isotope effect on the hydronium ion-catalyzed reaction, k(H(+))/k(D(+)) = 0.41, indicates that this process occurs by rapid and reversible protonation of the quinone methide on its carbonyl carbon atom, followed by rate-determining capture of the p-hydroxybenzyl carbocation so produced by water, while the magnitude of the rate constant on the uncatalyzed process indicates that this reaction occurs by simple nucleophilic addition of water to the methylene group of the quinone methide. p-Quinone methide also underwent hydronium ion-catalyzed and uncatalyzed nucleophilic addition reactions with chloride ion, bromide ion, thiocyanate ion, and thiourea. The solvent isotope effects on the hydronium ion-catalyzed processes again indicate that these reactions occurred by preequilibrium mechanisms involving a p-hydroxybenzyl carbocation intermediate, and assignment of a diffusion-controlled value to the rate constant for reaction of this cation with thiocyanate ion led to K(SH) = 110 M as the acidity constant of oxygen-protonated p-quinone methide. In a certain perchloric acid concentration range, the bromide ion reaction became biphasic, and least-squares analysis of the kinetic data using a double-exponential function provided k(Br(-)) = 3.8 x 10(8) M(-1) s(-1) as the rate constant for nucleophilic capture of the p-hydroxybenzyl carbocation by bromide ion, k(ionz) = 8.5 x 10(2) s(-1) for ionization of the carbon-bromine bond of p-hydroxybenzyl bromide, and K = 4.5 x 10(5) M(-1) as the equilibrium constant for the carbocation-bromide ion combination reaction, all in aqueous solution at 25 degrees C. Comparisons are made of the reactivity of p-quinone methide with p-quinone alpha,alpha-bis(trifluoromethyl)methide as well as p-quinone methide with o-quinone methide.
Chiang
Y
Y
Department of Chemistry, University of Toronto Toronto, Ontario M5S 3H6, Canada.
Kresge
A J
AJ
Zhu
Y
Y
D006842:Hydrocarbons, Brominated / Q000737:chemistry*; D045563:Indolequinones; D007211:Indoles / Q000737:chemistry*; D007700:Kinetics; D010636:Phenols / Q000737:chemistry*; D010782:Photolysis; D011809:Quinones / Q000737:chemistry*; D012996:Solutions; D014867:Water / Q000737:chemistry
D006842:Hydrocarbons, Brominated; D045563:Indolequinones; D007211:Indoles; D010636:Phenols; D011809:Quinones; D012996:Solutions; D014867:Water; C068040:quinone methide