Kinetics and mechanism of monomolecular heterolysis of framework compounds. VI. Dehydrobromination of 2-bromo-2-methyladamantane in acetonitrile
The kinetics of dehydrobromination of 2-bromo-2-methyladamantane in acetonitrile were studied in the presence of triphenylverdazyl as internal indicator; k/sub 25/ = 8.57 /times/ 10/sup /minus/5/ sec/sup /minus/1/, /Delta/H/sup /ne// 79 kJ/mole, /Delta/S/sup /ne// /minus/58 kJ/mole /times/ deg. Additions of water, phenols, lithium perchlorate, and bromides increase the reaction rate, and additions of nitrates and picrates reduce it. A similar pattern is observed in the dehydrobromination of tert-butyl bromide in acetonitrile. In the presence of tetraethylammonium chloride the heterolysis rate of 2-bromo-2-methyladamantane decreases, while that of tert-butyl bromide increases. The positive salt effect is explained by stabilization of the transition state by the salt, and the negative salt effect is explained by the reaction of the anion with the sterically separated or solvent-separated ion pair of the substrate.
- Research Organization:
- Kiev Polytechnical Institute (USSR)
- OSTI ID:
- 5887587
- Journal Information:
- J. Org. Chem. USSR (Engl. Transl.); (United States), Journal Name: J. Org. Chem. USSR (Engl. Transl.); (United States) Vol. 24:3; ISSN JOCYA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
ACETONITRILE
ADAMANTANE
ALKALI METAL COMPOUNDS
ALKANES
BROMIDES
BROMINATED ALIPHATIC HYDROCARBONS
BROMINE COMPOUNDS
CATALYTIC EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHLORINE COMPOUNDS
CHROMATOGRAPHY
CYCLOALKANES
DECOMPOSITION
DEHALOGENATION
DEHYDROGENATION
HALIDES
HALOGEN COMPOUNDS
HALOGENATED ALIPHATIC HYDROCARBONS
HYDROCARBONS
HYDROGEN COMPOUNDS
INDICATORS
KINETICS
LITHIUM BROMIDES
LITHIUM COMPOUNDS
LITHIUM HALIDES
LITHIUM PERCHLORATES
NITRILES
NMR SPECTRA
ORGANIC BROMINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXYGEN COMPOUNDS
PERCHLORATES
REACTION KINETICS
SEPARATION PROCESSES
SOLVENT PROPERTIES
SOLVOLYSIS
SPECTRA
STOICHIOMETRY
WATER