ISSN:
0941-1216
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Synthesis and Reactivity of tert-Butyl-(2-aryl-3-methyl-but-2-yl) Peroxidestert-Butyl-(2-aryl-3-methyl-but-2-yl) peroxides (2a-d) were prepared from t-BuOOH and corresponding 2-aryl-methyl-butan-2-ols (1a-d) (Ar:p-MeO—C6H4 (a); Ph (b); p-Cl—C6H4 (c); m-CF3—C6H4 (d)) and characterized by NMR, MS and elemental analysis.Kinetic data for the thermolysis of 2a-d in cumene as the solvent were determined at 110-140 °C and the products analyzed. The rate constants satisfy the Hammett equation with σ giving a ρ-value of -0.73. Oxidation of 2a-d at 80 °C gives the corresponding acetophenones 4, epoxides 6 and hydroperoxides 8. The products of the oxidation of 2a-2d were analysed after reduction of the reaction mixtures with LiAlH4. Relative reactivities of the tertiary C—H bonds of peroxides 2 were determined by competitive oxidations. They amount to 0.115-0.275 (with respect to the tertiary C—H bond of cumene)
Additional Material:
3 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/prac.19973390111
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