Dramatic Solvent Effects on the Absolute Rate Constants for Abstraction of the Hydroxylic Hydrogen Atom from tert-Butyl Hydroperoxide and Phenol by the Cumyloxyl Radical. The Role of Hydrogen Bonding

1995 ◽  
Vol 117 (10) ◽  
pp. 2929-2930 ◽  
Author(s):  
David V. Avila ◽  
K. U. Ingold ◽  
J. Lusztyk ◽  
W. H. Green ◽  
D. R. Procopio
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Atom ◽  
Solvent Effects ◽  
Rate Constants ◽  
Absolute Rate ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide ◽  
The Absolute

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.

The Fe(III)-catalyzed functionalization of saturated hydrocarbons by tert-butyl hydroperoxide: Mechanistic studies on the role of dioxygen

1992 ◽  
Vol 33 (38) ◽  
pp. 5473-5476 ◽  
Author(s):  
Derek H.R. Barton ◽  
Stéphane D. Bévière ◽  
Warinthorn Chavasiri ◽  
Darío Doller ◽  
Bin Hu
Keyword(s):  
Mechanistic Studies ◽  
Saturated Hydrocarbons ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Tert Butyl Hydroperoxide

Glutathione protects against exogenous oxidant injury to rabbit renal proximal tubules

1988 ◽  
Vol 255 (5) ◽  
pp. F874-F884
Author(s):  
J. M. Messana ◽  
D. A. Cieslinski ◽  
R. P. O'Connor ◽  
H. D. Humes
Keyword(s):  
Oxidant Stress ◽  
Glutathione Depletion ◽  
Plasma Membrane Permeability ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
Cation Homeostasis ◽  
Tert Butyl Hydroperoxide ◽  
Organ Systems ◽  
Nonprotein Thiols

Glutathione, comprising a major portion of cellular nonprotein thiols, plays a central role in a diverse group of cell metabolic functions. Glutathione and related enzyme systems have been shown to protect against both toxin and oxidant-induced injury in several organ systems. The role of glutathione in protecting renal epithelia against oxidant stress has not been investigated previously. We report here the response of enriched, isolated rabbit renal proximal tubule segments to oxidant stress induced by tert-butyl hydroperoxide. In addition, the effects of glutathione depletion by various biochemical means and of exogenous glutathione supplementation on the response of tubule segments to tert-butyl hydroperoxide exposure are described. Depletion of cell glutathione by several distinct methods potentiates oxidant-induced injury. Augmentation of cellular glutathione affords significant protection against exogenous oxidant stress. The protective effect of glutathione may reside in its ability, in conjunction with glutathione peroxidase, to arrest the propagation of lipid peroxidation and, therefore, to minimize alterations in plasma membrane permeability. The results of this study do not exclude the possibility that glutathione prevents tert-butyl hydroperoxide induced oxidation of critical sulfhydryl groups of catalytic or structural proteins associated with control of cell cation homeostasis. These results confirm the important role of glutathione in protecting renal tubular epithelia against oxidant stress.

scholarly journals tert-Butyl Hydroperoxide (tBHP)-Induced Lipid Peroxidation and Embryonic Defects Resemble Glucose-6-Phosphate Dehydrogenase (G6PD) Deficiency in C. elegans

2020 ◽  
Vol 21 (22) ◽  
pp. 8688
Author(s):  
Hung-Chi Yang ◽  
Hsiang Yu ◽  
Tian-Hsiang Ma ◽  
Wen-Ye Tjong ◽  
Arnold Stern ◽  
...  
Keyword(s):  
Lipid Peroxidation ◽  
G6pd Deficiency ◽  
Short Term ◽  
Butyl Hydroperoxide ◽  
Tert Butyl ◽  
C Elegans ◽  
Tert Butyl Hydroperoxide ◽  
Calcium Independent Phospholipase A2 ◽  
Glucose 6 Phosphate Dehydrogenase

G6PD is required for embryonic development in animals, as severe G6PD deficiency is lethal to mice, zebrafish and nematode. Lipid peroxidation is linked to membrane-associated embryonic defects in Caenorhabditis elegans (C. elegans). However, the direct link between lipid peroxidation and embryonic lethality has not been established. The aim of this study was to delineate the role of lipid peroxidation in gspd-1-knockdown (ortholog of g6pd) C. elegans during reproduction. tert-butyl hydroperoxide (tBHP) was used as an exogenous inducer. Short-term tBHP administration reduced brood size and enhanced germ cell death in C. elegans. The altered phenotypes caused by tBHP resembled GSPD-1 deficiency in C. elegans. Mechanistically, tBHP-induced malondialdehyde (MDA) production and stimulated calcium-independent phospholipase A2 (iPLA) activity, leading to disturbed oogenesis and embryogenesis. The current study provides strong evidence to support the notion that enhanced lipid peroxidation in G6PD deficiency promotes death of germ cells and impairs embryogenesis in C. elegans.

Absolute rate constants for hydrocarbon autoxidation. 25. Rate constants for hydrogen atom abstraction from alkanes by the tert-butylperoxy radical

1978 ◽  
Vol 56 (24) ◽  
pp. 3047-3053 ◽  
Author(s):  
J. H. B. Chenier ◽  
S. B. Tong ◽  
J. A. Howard
Keyword(s):  
Hydrogen Atom ◽  
Rate Constants ◽  
Kinetic Isotope Effect ◽  
Peroxy Radical ◽  
Hydrogen Atom Abstraction ◽  
Labile Hydrogen ◽  
Absolute Rate ◽  
Steric Strain ◽  
Kinetic Isotope ◽  
Tert Butyl Hydroperoxide

Rate constants for abstraction of secondary and tertiary hydrogens from structurally different alkanes by the tert-butylperoxy radical in solution at 30 °C have been determined by competitive experiments in the presence of tert-butyl hydroperoxide. Rate constants fall in the range 1 × 10−4to 9 × 10−4and 1 × 10−3–2 × 10−2 M−1 s−1 for secondary and tertiary aliphatic C—H bonds, respectively. The most reactive secondary hydrogen is, therefore, almost as reactive as the least reactive tertiary hydrogen. Differences in reactivity within a type of aliphatic C—H bond are governed by differences in steric hindrance to attack by the peroxy radical and by relief of steric strain upon removal of the labile hydrogen. Rate constants for reaction of perdeuterated methylcyclohexane and 3-methylpentane are much smaller than the values calculated from the maximum primary kinetic isotope effect for this reaction.

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