Mechanism of oxidation of alcohols with N-bromo succinimide

1969 ◽  
Vol 47 (4) ◽  
pp. 694-697 ◽  
Author(s):  
N. Venkatasubramanian ◽  
V. Thiagarajan
Keyword(s):  
Secondary Alcohols ◽  
Cyclic Mechanism ◽  
Oxidation Of Alcohols ◽  
Mechanism Of Oxidation ◽  
Cis And Trans ◽  
Kinetics Of ◽  
Electron Withdrawing Substituents

The kinetics of the oxidation of a number of aliphatic and aromatic secondary alcohols with N-bromo succinimide has been investigated. Electron-withdrawing substituents retard the reaction considerably and electron-releasing substituents increase the rate of oxidation. The Taft ρ* value is −2.56. Cis- and trans-4-t-butyl cyclohexanols are oxidized at nearly the same rates. There is also a good correlation between the rates of the NBS oxidations and Br2 oxidations of these alcohols. The results are interpreted in terms of a cyclic mechanism involving a rate-determining abstraction of the alpha hydrogen as a hydride anion.

Kinetics and mechanism of oxidation of DL-α-alanine by permanganate ion in acid perchlorate media

1991 ◽  
Vol 69 (12) ◽  
pp. 2018-2023 ◽  
Author(s):  
Refat M. Hassan
Keyword(s):  
Amino Acids ◽  
Ionic Strength ◽  
Acid Solution ◽  
Second Order ◽  
Perchloric Acid Solution ◽  
Oxidation Reduction ◽  
Initial Stage ◽  
Aqueous Perchloric Acid ◽  
Mechanism Of Oxidation ◽  
Kinetics Of

The kinetics of permanganate oxidation of DL-α-alanine in aqueous perchloric acid solution at a constant ionic strength of 2.0 mol dm−3 has been investigated spectrophotometrically. The reaction was found to show second-order kinetics overall with respect to each of the reactants in the slow initial stage; the second-order kinetics are not, however, maintained throughout the relatively fast final stage of reaction. The added salts lead to the prediction that Mn(III) and (or) Mn(IV) play a very important role in the reaction kinetics. A tentative mechanism consistent with the kinetics is discussed. Key words: kinetics, oxidation, reduction, amino acids, permanganate.

Kinetics of the Isomerization of 1-Decene to cis- and trans-2-Decene

1995 ◽  
Vol 60 (13) ◽  
pp. 4255-4257 ◽  
Author(s):  
Mario L. Aimar ◽  
Rita H. de Rossi
Keyword(s):  
Cis And Trans ◽  
Kinetics Of

Revisiting Sodium Hypochlorite Pentahydrate (NaOCl·5H2O) for the Oxidation of Alcohols in Acetonitrile without Nitroxyl Radicals

Synlett ◽  
2018 ◽  
Vol 29 (18) ◽  
pp. 2404-2407 ◽  
Author(s):  
Tsunehisa Hirashita ◽  
Yuto Sugihara ◽  
Shota Ishikawa ◽  
Yohei Naito ◽  
Yuta Matsukawa ◽  
...  
Keyword(s):  
Sodium Hypochlorite ◽  
Nitroxyl Radicals ◽  
Secondary Alcohols ◽  
Primary Alcohols ◽  
Oxidation Of Alcohols

Sodium hypochlorite pentahydrate (NaOCl·5H2O) is capable of oxidizing alcohols in acetonitrile at 20 °C without the use of catalysts. The oxidation is selective to allylic, benzylic, and secondary alcohols. ­Aliphatic primary alcohols are not oxidized.

Oxidation of secondary alcohols and ethers by dimethyldioxirane

1999 ◽  
Vol 77 (3) ◽  
pp. 308-312 ◽  
Author(s):  
Alfons L Baumstark ◽  
Franci Kovac ◽  
Pedro C Vasquez
Keyword(s):  
Oxygen Atom ◽  
Methyl Ether ◽  
Radical Pair ◽  
Parent Compound ◽  
Activation Parameters ◽  
Silyl Ether ◽  
Secondary Alcohols ◽  
Benzyl Alcohols ◽  
Oxidation Of Alcohols ◽  
Direct Abstraction

The oxidation of several series of secondary alcohols 2-9, ethers 10-17, and related derivatives 18 and19, by dimethyldioxirane, 1, in acetone at 25°C produced the corresponding ketones in good to excellent yields for all but two cases. (The exceptions: oxidation of 1-methoxy-2-methyl-1-phenylpropane (48%) and 1-methoxy-2,2-dimethyl-1-phenylpropane (24%).) The oxidation of the secondary alcohols was found to yield k2 values that were roughly 10-fold greater than those of the corresponding methyl ethers. The rate constant for oxidation of a silyl ether was slightly lower than that for the corresponding methyl ether while that for the ester derivative was roughly half the value. For oxidation of alcohols and methyl ethers, the k2 values became smaller as the R " series (Me, Et, nPr, iPr, and tBu) increased in steric bulk (ρ* = 1.7; r = 0.998 and ρ* = 3.2; r = 0.95, respectively). The Hammett study for the oxidation of the methyl ethers of α-methyl-p-benzyl alcohols (10, 20-25) yielded a ρ value of -0.74. The activation parameters for oxidation of the parent compound of the ether series (1-methoxy-1-phenylethane) were ΔH‡ = 14.8 ± 0.5 kcal/mol, ΔS‡ = -21.9 eu, ΔG‡ = 21.3 kcal/mol, k2 (25°C) = 1.6 × 10-3 M-1 s-1. The mechanistic aspects of the oxidation are discussed in relation to two mechanistic extremes: (a) direct insertion of the oxygen atom into the C—H bond and (b) direct abstraction of the H by dimethyldioxirane to yield a caged-radical pair, with subsequent coupling to hemi-ketal intermediates that fragment to yield acetone, alcohol or water, and ketone as the final products.Key words: dimethyldioxirane, oxidation.

Kinetics of oxidation of alcohols with tetramethylammonium fluorochromate

2005 ◽  
Vol 54 (2) ◽  
pp. 462-465 ◽  
Author(s):  
F. Gharib ◽  
K. Zare ◽  
Sh. Ghammami ◽  
R. Ebrahimi
Keyword(s):  
Kinetics Of Oxidation ◽  
Oxidation Of Alcohols ◽  
Kinetics Of
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