The alkylated benzoquinonepropionic acid 3, 3-(3',6'-dioxo-2',4',5'-trimethylcyclohexa-l',4'-diene)-3,3-dimethylpropionic acid, while stable in anhydrous solvents, cyclizes in the presence of water to a spirolactone 5, 4,4,7,8,10-pentamethyl-l-oxaspiro[4.5]dec-7-ene-2,6,9-trione. The pH-dependent equilibrium mixture contains 87% spirolactone at pH 4 and 1 Kinetic analysis (at 30") shows the ring-opening elimination step to be subject to catalysis by buffer base, proton transfer from 5 to the buffer being the rate-limiting step in the range studied. Conjugate addition involves, at low buffer concentration, a rate-limiting proton transfer from buffer acid to the carbanion of 5, the cyclic counterpart of the anion of 3. At moderate buffer concentrations, the ratelimiting dependence on buffer acid disappears as proton transfer becomes faster than the initial addition step. At still higher concentrations of buffer, the rate of lactone formation falls again, for reasons still undetermined. Although the existence of a carbanion species could not be shown by deuterium exchange, the change in ratedetermining step makes it a mandatory intermediate in the reaction. The analogous brominated quinonepropionic acid 11, 3-(3',6'-dioxo-2',4'-dibromo-5'-methylcyclohexa-l',4'-diene)-3,J-dimethylpropionic acid, cyclizes to the spirolactone 12, 8,10-dibromo-4,4-dimethyl-l-oxaspiro[4.5]dec-7-ene-2,6,9-trione, so rapidly it could not be isolated or even detected under the reaction conditions. Unless 4,4,5-trisubstitution (the trialkyl lock) is present, no conjugate addition can be detected. The unique reactions of 3 and 11 are attributed to the severe conformationrestricting ability of the "lock" and to secondary phenomena resulting therefrom. This reaction provides a useful model for enzyme-catalyzed conjugate addition and elimination.at pH 8. n preceding papers of this series2 we have shown how (20) J. Miller, "Aromatic Nucleophilic Substitution," Elsevier, New York, N. Y., 1968, p 303. (21) Compound 17 is also unstable above pH 8.