Transition state effects in the acid-catalyzed hydrolysis of 5-methoxyacenaphthylene 1,2-oxide: implications for the mechanism of acid-catalyzed hydrolysis of cyclopenta[cd]pyrene 3,4-oxide.
5-Methoxyacenaphthylene 1,2-oxide (5) was synthesized by the reaction of 5-methoxyacenaphthylene with dimethyldioxirane. The rates and products from the acid-catalyzed and pH-independent reactions of 5 in 50:50 dioxane/water have been determined. The half-life of the pH-independent reaction of this very reactive epoxide in 50:50 dioxane/water is only 22 s. Acid-catalyzed hydrolysis of 5 in 50:50 dioxane/water yields 62% of cis diol 6, 37% of trans diol 7, and approximately 1% of 5-methoxy-1,2-dihydroacenaphthylen-1-one (8). The pH-independent reaction of 5 yields mostly ketone 8 (94%), along with minor amounts of cis and trans diols. The relative stabilities of cis and trans diols 6 and 7 were determined by treating either cis or trans diol with perchloric acid in water solutions and following the approach to an equilibrium cis/trans diol mixture as a function of time. At equilibrium, the ratio of cis and trans diols is 19:81, which establishes that trans diol 7 is more stable than cis diol 6. The acid-catalyzed hydrolysis of epoxide 5 therefore yields the less stable cis diol as the major product. It is concluded that transition state effects therefore selectively stabilize the transition state for attack of water on the intermediate carbocation leading to the less stable cis diol. These results suggest that transition state effects are also responsible for formation of the major cis diol in the acid-catalyzed hydrolysis of cyclopenta[cd]pyrene 3,4-oxide, which has a cyclopenta-fused ring similar to that in 5.
Department of Chemistry, University of Maryland, Baltimore County, 1000 Hilltop Circle, Baltimore, Maryland 21250, USA.
Chumang
C
Zhao
Dale L
DL
Whalen
D000073:Acenaphthenes / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D018360:Crystallography, X-Ray; D004146:Dioxanes / Q000737:chemistry; D004852:Epoxy Compounds / Q000737:chemistry; D006860:Hydrogen Bonding; D006863:Hydrogen-Ion Concentration; D006868:Hydrolysis; D008958:Models, Molecular; D015394:Molecular Structure; D010087:Oxides / Q000138:chemical synthesis* / Q000737:chemistry; D011721:Pyrenes / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D013997:Time Factors; D014867:Water / Q000737:chemistry
C510601:5-methoxy-1,2-dihydroacenaphthylen-1-one; C510600:5-methoxyacenaphthylene 1,2-oxide; D000073:Acenaphthenes; D004146:Dioxanes; D004852:Epoxy Compounds; D010087:Oxides; D011721:Pyrenes; D014867:Water; C025223:1,4-dioxane; C064455:dimethyldioxirane; C027599:cyclopenta(cd)pyrene 3,4-oxide