The reactivity of tert-butylperoxy radicals with respect to aldehydes, amines, and ethers in solution. The importance of polar effect
✍ Scribed by L. A. Tavadyan; V. A. Mardoyan; M. V. Musaelyan
- Publisher
- John Wiley and Sons
- Year
- 1996
- Tongue
- English
- Weight
- 678 KB
- Volume
- 28
- Category
- Article
- ISSN
- 0538-8066
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✦ Synopsis
The data about the rate constants of the hydrogen atom abstraction for the reactions of tertbutylperoxy radicals (t-BuO; ) 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 o n 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 rractivity 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 ( I ) . the parameter, characterizing a stereoelectronic effect. and the energy of C-H 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.