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The reactivity of tert ‐butylperoxy radicals with respect to aldehydes, amines, and ethers in solution. The importance of polar effect
Author(s) -
Tavadyan L. A.,
Mardoyan V. A.,
Musaelyan M. V.
Publication year - 1996
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/(sici)1097-4601(1996)28:8<555::aid-kin1>3.0.co;2-u
Subject(s) - chemistry , reactivity (psychology) , heteroatom , radical , reaction rate constant , solvent , solvent effects , computational chemistry , photochemistry , organic chemistry , kinetics , alkyl , medicine , alternative medicine , physics , pathology , quantum mechanics
The data about the rate constants of the hydrogen atom abstraction for the reactions of tert ‐butylperoxy radicals ( t ‐BuO˙ 2 ) with aldehydes, ethers, and aliphatic amines are summarized in the present work. The rate constants were measured by using a kinetic EPR‐technique with a pulse introduction of the reagents. The problem of the reactivity has been discussed based on the data about the reaction rate constants, the influence of medium on their values, and the correlation dependence. It has been concluded that the complete description of the reactivity of organic compounds, containing heteroatoms, with respect to peroxy radical is possible, if to take into account simultaneously the various parameters, which influence the reactivity, such as, the ionization potential (1), the parameter, characterizing a stereoelectronic effect, and the energy of CH bond. The latter for the cyclic compounds is determined by Brown's rule of “I tension.” Molecule of organic compound, containing heteroatom, may be both activated and passivated by a solvent with respect to tert ‐butylperoxy radical, dependent on a change of the electron donating capacity of organic compound in a given medium. © 1996 John Wiley & Sons, Inc.