Flash photolytic generation of ortho-quinone methide in aqueous solution and study of its chemistry in that medium.
Flash photolysis of o-hydroxybenzyl alcohol, o-hydroxybenzyl p-cyanophenyl ether, and (o-hydroxybenzyl)trimethylammonium iodide in aqueous perchloric acid and sodium hydroxide solutions, and in acetic acid and biphosphate ion buffers, produced o-quinone methide as a short-lived transient species that underwent hydration back to benzyl alcohol in hydrogen-ion catalyzed (k(H+) = 8.4 x 10(5) M(-1) s(-1)) and hydroxide-ion catalyzed (k(HO)- = 3.0 x 10(4) M(-1) s(-1)) reactions as well as an uncatalyzed (k(UC) = 2.6 x 10(2) s(-1)) process. The hydrogen-ion catalyzed reaction gave the solvent isotope effect k(H+)/k(D)+ = 0.42, whose inverse nature indicates that this process occurs by rapid and reversible equilibrium protonation of the carbonyl oxygen atom of the quinone methide, followed by rate-determining capture of the carbocation so produced by water. The magnitude of the rate constant of the uncatalyzed reaction, on the other hand, indicates that this process occurs by simple nucleophilic addition of water to the methylene group of the quinone methide. Decay of the quinone methide is also accelerated by acetic acid buffers through both acid- and base-catalyzed pathways, and quantitative analysis of the reaction products formed in these solutions shows that this acceleration is caused by nucleophilic reactions of acetate ion rather than by acetate ion assisted hydration. Bromide and thiocyanate ions also accelerate decay of the quinone methide through both hydrogen-ion catalyzed and uncatalyzed pathways, and the inverse nature of solvent isotope effects on the hydrogen-ion catalyzed reactions shows that these reactions also occur by rapid equilibrium protonation of the quinone methide carbonyl oxygen followed by rate-determining nucleophilic capture of the ensuing carbocation. Assignment of an encounter-controlled value to the rate constant for the rate-determining step of the thiocyanate reaction leads to pK(a) = -1.7 for the acidity constant of the carbonyl-protonated quinone methide.
Chiang
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Y
Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6, Canada.
Kresge
A J
AJ
Zhu
Y
Y
D019342:Acetic Acid / Q000737:chemistry; D001965:Bromides / Q000737:chemistry; D002021:Buffers; D002384:Catalysis; D002851:Chromatography, High Pressure Liquid; D004987:Ethers / Q000737:chemistry; D045563:Indolequinones; D007211:Indoles / Q000138:chemical synthesis* / Q000737:chemistry*; D007554:Isotopes / Q000737:chemistry; D007700:Kinetics; D015394:Molecular Structure; D010472:Perchlorates / Q000737:chemistry; D010636:Phenols / Q000737:chemistry; D010777:Photochemistry / Q000379:methods; D011809:Quinones / Q000138:chemical synthesis* / Q000737:chemistry*; D012972:Sodium Hydroxide / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet; D013237:Stereoisomerism; D013329:Structure-Activity Relationship; D013861:Thiocyanates / Q000737:chemistry
C434337:(o-hydroxybenzyl)trimethylammonium iodide; D001965:Bromides; D002021:Buffers; D004987:Ethers; D045563:Indolequinones; D007211:Indoles; D007554:Isotopes; D010472:Perchlorates; D010636:Phenols; D011809:Quinones; D013861:Thiocyanates; C434336:o-hydroxybenzyl p-cyanophenyl ether; C068040:quinone methide; D012972:Sodium Hydroxide; C031760:thiocyanate; D019342:Acetic Acid