Hydrolysis of strained bridgehead bicyclic vinyl ethers and sulfides
- Univ. of Toronto, West Hill, Ontario
Rates of hydrolysis of the bridgehead bicyclic vinyl ether 9-oxabicyclo(3.3.1)non-1-ene(6) and its vinyl sulfide counterpart 9-thiabicyclo(3.3.1)non-1-ene(7), catalyzed by the hydronium ion, were measured in H/sub 2/O and in D/sub 2/O solution. These data give isotope effects, k/sub H//k/sub D/ = 2.4 and 1.9 respectively, which show that these reactions occur by the normal, rate-determining carbon protonation, mechanism. The vinyl ether 6 is less reactive than its olefin analogue, bicyclo(3.3.1)non-1-ene (relative rate 1:1/1400), as may have been expected for a constrained bicyclic system such as this, where stabilization of the bridgehead carbocation intermediate by conjugation with oxygen is severely impaired. The vinyl sulfide 7, however, is even less reactive than the vinyl ether (relative rates 1:1/140); this is a remarkable result in view of the fact that conjugation between the sulfur atom and the cationic center is presumably also strongly inhibited. 1 figure, 3 tables.
- OSTI ID:
- 5541853
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 101:23; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400202* -- Isotope Effects
Isotope Exchange
& Isotope Separation
400302 -- Organic Chemistry-- Isotope Effects-- (-1987)
ALKENES
CARBON
CHALCOGENIDES
CHARGED PARTICLES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CRYOGENIC FLUIDS
DATA
DATA FORMS
DECOMPOSITION
DEUTERIUM
ELEMENTS
ETHERS
EXPERIMENTAL DATA
FLUIDS
HEAVY WATER
HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
HYDROLYSIS
INFORMATION
IONS
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
LYSIS
MOLECULAR IONS
MONOMERS
NONMETALS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXONIUM IONS
OXYGEN
OXYGEN COMPOUNDS
REACTION KINETICS
SOLVOLYSIS
STABLE ISOTOPES
SULFIDES
SULFUR COMPOUNDS
TABLES
VINYL MONOMERS
WATER