Aromatic desulfonation: determination of reaction mechanism on the basis of the theory of activity coefficients of the transition state and the Cox-Yates excess acidity function
The mechanism of the desulfonation (hydrolysis) of mesitylenesulfonic acid in sulfuric acid (0-80 wt. %) at 25/degree/C was analyzed by means of the theory of the activity coefficients of the transition state (f/sub S/ne///sup */) and the excess acidity function (the X function). The dependence of the log (f/sub S/ne///sup */) values on the concentration of the desulfonating sulfuric acid, the linear correlation between the effective reaction rate constants (in the form of log k/sub h.eff/-log c/sub H/sup +//) and the X function of the medium, and the degree of proton transfer to the substrate in the transition state (/alpha/ = 0.88 /plus minus/0.04), calculated from the angular coefficient of this correlation, which agrees with data on the reagent-solvent kinetic isotope effect (k/sub H//k/sub D/ = 2.8 /plus minus/ 0.3), indicate unambiguously a mechanism of the A-S/sub E/sup 2// type.
- Research Organization:
- Ivanovo State Univ., (USSR)
- OSTI ID:
- 5887157
- Journal Information:
- J. Org. Chem. USSR (Engl. Transl.); (United States), Journal Name: J. Org. Chem. USSR (Engl. Transl.); (United States) Vol. 24:4; ISSN JOCYA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201 -- Chemical & Physicochemical Properties
400202* -- Isotope Effects
Isotope Exchange
& Isotope Separation
ACTIVATION ENERGY
ALKYLATED AROMATICS
AROMATICS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHROMATOGRAPHY
DECOMPOSITION
DEUTERATION
DEUTERIUM
DEUTERIUM COMPOUNDS
ENERGY
ESTERS
HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
HYDROGEN TRANSFER
HYDROLYSIS
INORGANIC ACIDS
ISOTOPE EFFECTS
ISOTOPES
ISOTOPIC EXCHANGE
KINETICS
LIGHT NUCLEI
LYSIS
MATHEMATICAL MODELS
MESITYLENE
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PH VALUE
REACTION KINETICS
REMOVAL
SEPARATION PROCESSES
SOLVOLYSIS
STABLE ISOTOPES
SULFONES
SULFONIC ACID ESTERS
SULFURIC ACID