Polyfunctional peroxides from tert-butyl hydroperoxide-loaded autoxidations of polyunsaturated substrates and an assessment of the rate constants for allylic peroxyl radical rearrangements and peroxyl radical ring closures

1992 ◽  
pp. 1270 ◽  
Author(s):  
John L. Courtneidge
Keyword(s):  
Rate Constants ◽  
Peroxyl Radical ◽  
Radical Ring ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide ◽  
Radical Rearrangements

Absolute rate constants for hydrocarbon autoxidation. 24. Rate constants and Arrhenius parameters for reaction of tert-butylperoxy radicals with 3-methylpentane

1978 ◽  
Vol 56 (2) ◽  
pp. 170-175 ◽  
Author(s):  
J. A. Howard ◽  
J. H. B. Chenier ◽  
D. A. Holden
Keyword(s):  
Rate Constants ◽  
Arrhenius Equation ◽  
Absolute Rate ◽  
Reaction Products ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
A Value ◽  
Tert Butyl Hydroperoxide ◽  
Reduction With Triphenylphosphine ◽  
Major Reaction

Autoxidation of 3-methylpentane in the presence of tert-butyl hydroperoxide gives, after reduction with triphenylphosphine, 3-methyl-3-pentanol and 3-methyl-2-pentanol as the major reaction products. The overall rate constant for reaction of (CH3)3COO· with this substrate at 30 °C is 0.008 ± 0.001 M−1 s−1 which consists of k/tertiary C—H = 0.007 ± 0.001 M−1 s−1 and k/secondary C—H = 0.0002 ± 0.0001 M−1 s−1. The products from cooxidation of cumene and 3-methylpentane in the presence of tert-butyl hydroperoxide are formed in yields which are consistent with these rate constants relative to a value of 0.16 M−1 s−1 for cumene. The Arrhenius equations for reaction of (CH3)3COO• with the t-C—H and s-C—H of 3-methylpentane relative to the Arrhenius equation for reaction of (CH3)3COO• with cumene (log (k10/M−1 s−1) = (8.7 ± 0.3) − (13.2 ± 0.4)/θ) are[Formula: see text]respectively, where θ = 2.303 RT kcal mol−1.

Absolute rate constants for hydrocarbon autoxidation. 29. Rate constants for abstraction of primary aliphatic hydrogens from 2,2-dimethylbutane by the tert-butylperoxy radical

1980 ◽  
Vol 58 (24) ◽  
pp. 2808-2812 ◽  
Author(s):  
J. A. Howard ◽  
J. H. B. Chenier
Keyword(s):  
Rate Constant ◽  
Rate Constants ◽  
Methyl Groups ◽  
Absolute Rate ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide

Rate constants for abstraction of primary and secondary hydrogens from 2,2-dimethylbutane by the tert-butylperoxy radical at temperatures from 323 to 353 K have been determined from autoxidations and co-autoxidations in the presence of tert-butyl hydroperoxide. At 333 K the rate constant for abstraction of a secondary hydrogen is ~1.5 × 10−3 M−1 s−1 and the rate constants for abstraction of a primary hydrogen from the tert-butyl and methyl groups of 2,2-dimethylbutane are ~4 × 10−5 and ~6 × 10−5 M−5 s−1 respectively.

Tetrabutylammonium Iodide Catalyzed Synthesis of Allylic Ester with tert-Butyl Hydroperoxide as an Oxidant

2012 ◽  
Vol 14 (13) ◽  
pp. 3384-3387 ◽  
Author(s):  
Erbo Shi ◽  
Ying Shao ◽  
Shulin Chen ◽  
Huayou Hu ◽  
Zhaojun Liu ◽  
...  
Keyword(s):  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide ◽  
Tetrabutylammonium Iodide
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