The Mechanism of the Chromic Acid Oxidation of Isopropyl Alcohol. The Chromic Acid Ester<sup>1</sup>

Holloway, Frank; Cohen, Merrill; Westheimer, F. H.

doi:10.1021/ja01145a025

Cited by 53 publications

(23 citation statements)

References 14 publications

(6 reference statements)

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“…[44,45] However, no such complex has been observed with perruthenate (Scheme 2a). It is generally assumed that alcohols are oxidized by perruthenate through the formation of an alkoxide or organometallic transition state complex.…”

Section: Resultsmentioning

confidence: 99%

“…[32] Lee et al [31][32][33] found that tetrahydrofuran (THF) was oxidized much more slowly than isopropyl alcohol. West-heimer et al [44,45] found a straightforward explanation of this difference when investigating chromic acid oxidations. That is, the alcohol is oxidized by formation of an alkoxide intermediate, whereas this not possible for an ether.…”

Section: Resultsmentioning

confidence: 99%

“…The classic example highlighting this type of mechanism is the chromic acid oxidation of isopropyl alcohol for which the proposed isopropyl chromate intermediate was isolated. [44,45] However, no such complex has been observed with perruthenate (Scheme 2a).…”

Section: Resultsmentioning

confidence: 99%

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Hydrogen‐Bonding Interactions in the Ley–Griffith Oxidation: Practical Considerations for the Synthetic Chemist

et al. 2018

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The Ley–Griffith oxidation, which is catalyzed by tetra‐n‐propylammonium perruthenate (TPAP, nPr4N[RuO4]), is a popular method for not only controlled oxidation of primary alcohols to aldehydes, but also a host of other synthetically useful transformations. While the fundamental reaction mechanism has recently been elucidated, several key hydrogen‐bonding interactions between the reagents were implicated but not investigated. Herein the prevalence of H‐bonding between the co‐oxidant N‐methylmorpholine N‐oxide (NMO), the alcohol substrate, water and the perruthenate catalyst is established. These observations help to rationalize the importance of drying the reagents and lead to several practical suggestions.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Hydrogen‐Bonding Interactions in the Ley–Griffith Oxidation: Practical Considerations for the Synthetic Chemist

et al. 2018

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“…The first-order rate con stant for the reaction with water, extrapolated to zero buffer concentration, Oxidation of organic compounds by inorganic oxidants.-The kinetics of oxidation of isopropyl alcohol by chromic acid has been investigated by Holloway, Cohen & Westheimer (176). In further support of the authors' hy pothesis that the reaction proceeds through the formation of an intermedi ate chromate ester, they have isolated a stable solution of yellow di-iso propyl �hromate.…”

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confidence: 98%

Reaction Kinetics

Powell¹

1952

Annu. Rev. Phys. Chem.

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Since scientific papers which could be catalogued as reaction kinetics are currently being published at a rate of more than a thousand per year, a simple bibliography of one year's pUblications would fill the space allotted this review. Fortunately for the reviewer, many papers fall into special fields such as photochemistry, polymerization, contact catalysis, isotopic studies, or biochemical kinetics, which will be reviewed separately in the present volume or succeeding volumes of the Annual Review of Physical Chemistry.

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“…The classic example of this type of mechanism is the chromic acid oxidation of isopropyl alcohol for which the proposed isopropyl chromate intermediate was isolated. [322][323] However, no such complex has been observed with perruthenate.…”

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confidence: 99%

Understanding the mechanisms of transition metal catalysed redox reactions

Zerk¹

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Transition metal complexes catalyse a number of important synthetic chemical reactions. Two such reactions which rely on copper and ruthenium complexes respectively are atom transfer radical polymerisation (ATRP) and the Ley-Griffith oxidation of alcohols.In ATRP a copper(I) complex bearing a chelate ligand 'L' homolytically cleaves the carbon-halogen bond of an organo halide initiator (R-X) to produce an alkyl radical and the corresponding copper(II)-halido complex (Cu I L + RX → R• + Cu II LX). The reverse reaction is coined 'deactivation' and provides control to the process by keeping the concentration of the radical low. It is experimentally difficult to determine the rate of this reaction because it is so fast. Herein, a new method for measuring the rate of deactivation is developed using cyclic voltammetry coupled to simulations. The mechanism of deactivation is also unknown and this aspect is investigated by a kinetic study of halide substitution reactions on three ATRP-relevant Cu ). EPR spectroscopy alsoshows that NMO forms an outer-sphere associated complex with perruthenate which may be important in facilitating this reaction. Finally, synergistic EPR and UV-vis spectroscopy demonstrate that even with a large excess of NMO, a small amount of ruthenium dioxide still forms during the Ley-Griffith oxidation and acts as an accelerant for the reaction -i.e. the reaction is auto-catalytic. Declaration by author

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The Mechanism of the Chromic Acid Oxidation of Isopropyl Alcohol. The Chromic Acid Ester¹

Cited by 53 publications

References 14 publications

Hydrogen‐Bonding Interactions in the Ley–Griffith Oxidation: Practical Considerations for the Synthetic Chemist

Hydrogen‐Bonding Interactions in the Ley–Griffith Oxidation: Practical Considerations for the Synthetic Chemist

Reaction Kinetics

Understanding the mechanisms of transition metal catalysed redox reactions

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The Mechanism of the Chromic Acid Oxidation of Isopropyl Alcohol. The Chromic Acid Ester1

Cited by 53 publications

References 14 publications

Hydrogen‐Bonding Interactions in the Ley–Griffith Oxidation: Practical Considerations for the Synthetic Chemist

Hydrogen‐Bonding Interactions in the Ley–Griffith Oxidation: Practical Considerations for the Synthetic Chemist

Reaction Kinetics

Understanding the mechanisms of transition metal catalysed redox reactions

Contact Info

Product

Resources

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The Mechanism of the Chromic Acid Oxidation of Isopropyl Alcohol. The Chromic Acid Ester¹