Abstract
Hydrotrioxides (HT), ROOOH, from isopentane, 1,4-dimethylcyclohexane, 1,3-dimethylcyclohexane, decalin and triphenylmethane were synthesized for the first time by low-temperature ozonation of the corresponding hydrocarbons on a silica surface. Thermal decomposition of hydrotrioxides is accompanied by the formation of radicals and by infrared and visible chemiluminescence (CL). In solution the HTs form self-associates and react reversibly with the solvent (acetone) producing Bayer-Villiger type intermediates (unsymmetrical dialkyl trioxides). These reactions cause a complex character of the decomposition kinetics of HTs, as evidenced by monitoring the dependence of CL intensity on time. Activation parameters of thermal decomposition of HTs show a compensation effect (logA vs EA) which describes well the available experimental and theoretical data for the homolysis of organic trioxides.
Original language | English (US) |
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Pages (from-to) | 87-96 |
Number of pages | 10 |
Journal | Journal of Physical Organic Chemistry |
Volume | 13 |
Issue number | 2 |
DOIs | |
State | Published - Feb 2000 |
Externally published | Yes |
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Organic Chemistry
Keywords
- Association
- Chemiluminescence
- Free radicals
- Hydrogen bonding
- Hydrotrioxides
- Mechanism
- Ozone
- Silica gel
- Singlet oxygen