Kinetics and mechanism of monomolecular heterolysis of framework compounds. IV. Ionization of 1-adamantyl iodide in propylene carbonate

Journal Article · Thu Sep 10 00:00:00 EDT 1987 · J. Org. Chem. USSR (Engl. Transl.); (United States)

OSTI ID:7199823

Ponomareva, E A; Tarasenko, P V; Yurchenko, A G; Dvorko, G F

The heterolysis of 1-iodoadamantane in propylene carbonate was studied preparatively and kinetically; v = k (1-AdI), k/sub 25/ = 2.50 x 10/sup -8/ sec/sup -1/, ..delta..H/sup does not equal/ = 90.9 kJ/mole, ..delta..S/sup does not equal/ = -85.5 J/mole x deg. Additions of water, LiClO/sub 4/, and Et/sub 4/N/sup +/ClO/sub 4//sup -/ increase and additions of Et/sub 4/N/sup +/I/sup -/, LiBr, Et/sub 4/N/sup +/Br..sqrt.., Bu/sub 4/N/sup +/Br/sup -/, Et/sup 4/N/sup +/Cl/sup -/, LiPic, and Et/sub 4/N/sup +/Pic/sup -/ reduce the reaction rate. It is suggested that a sterically separated ion pair is formed in the rate-controlling stage and is quickly transformed into a solvent-separated ion pair, which then gives the reaction products. The negative salt effect is due to the action of the salt on the sterically separated ion pair.

• Research Organization: Kiev Polytechnic Institute (USSR)
• OSTI ID: 7199823
• Journal Information: J. Org. Chem. USSR (Engl. Transl.); (United States), Journal Name: J. Org. Chem. USSR (Engl. Transl.); (United States) Vol. 23:4; ISSN JOCYA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
640302 -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
ACTIVATION ENERGY
ADAMANTANE
ALKALI METAL COMPOUNDS
ALKANES
BROMINATED ALIPHATIC HYDROCARBONS
CARBONIC ACID ESTERS
CHEMICAL REACTION KINETICS
CHEMICAL SHIFT
CHLORIDES
CHLORINATED ALIPHATIC HYDROCARBONS
CHLORINE COMPOUNDS
COUPLING
COUPLING CONSTANTS
CYCLOALKANES
DISSOCIATION
ENERGY
ESTERS
HALIDES
HALOGEN COMPOUNDS
HALOGENATED ALIPHATIC HYDROCARBONS
HYDROCARBONS
INFRARED SPECTRA
INTERMEDIATE COUPLING
IODINATED ALIPHATIC HYDROCARBONS
IONIZATION
IONIZATION POTENTIAL
J-J COUPLING
KINETICS
LITHIUM CHLORIDES
LITHIUM COMPOUNDS
LITHIUM HALIDES
LITHIUM PERCHLORATES
LYSIS
NMR SPECTRA
ORGANIC BROMINE COMPOUNDS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC IODINE COMPOUNDS
OXYGEN COMPOUNDS
PERCHLORATES
REACTION KINETICS
SPECTRA