Jones oxidation

Jones reagent will convert primary and secondary alcohols to aldehydes and ketones, respectively. Depending on the reaction conditions, the aldehydes may then be converted to carboxylic acids. For oxidations to the aldehydes and ketones, two equivalents of chromic acid oxidize three equivalents of the alcohol:

: 2 HCrO₄⁻ + 3 RR'C(OH)H + 8 H⁺ + 4 H₂O → 2 [Cr(H₂O)₆]³⁺ + 3 RR'CO

For oxidation of primary alcohols to carboxylic acids, 4 equivalents of chromic acid oxidize 3 equivalents of the alcohol. The aldehyde is an intermediate.

:4 HCrO₄⁻ + 3 RCH₂OH + 16 H⁺ + 11 H₂O → 4 [Cr(H₂O)₆]³⁺ + 3 RCOOH

The inorganic products are green, characteristic of chromium(III) aquo complexes.

Like many other oxidations of alcohols by metal oxides, the reaction proceeds via the formation of a mixed chromate ester:{{March6th}}{{cite book|author1=Ley, S. V. |author2=Madin, A. |title = Comprehensive organic synthesis|year = 1991|volume=7|pages = 253–256 |editor1=B. M. Trost |editor2=I. Fleming |publisher=Pergamon Press|place=Oxford}} These esters have the formula CrO₃(OCH₂R)⁻

:CrO₃(OH)⁻ + RCH₂OH → CrO₃(OCH₂R)⁻ + H₂O

Like conventional esters, the formation of this chromate ester is accelerated by the acid. These esters can be isolated when the alcohol is tertiary because these lack the α hydrogen that would be lost to form the carbonyl. For example, using tert-butyl alcohol, one can isolate tert-butyl chromate ((CH₃)₃CO)₂CrO₂), which is itself a good oxidant.Fillmore Freeman, "Di-tert-butyl Chromate" Encyclopedia of Reagents for Organic Synthesis, 2001, John Wiley & Sons, Ltd. {{doi|10.1002/047084289X.rd059m}}

For those structures with hydrogen alpha to the oxygen, the chromate esters degrade, releasing the carbonyl product and an ill-defined Cr(IV) product:

:CrO₃(OCH₂R)⁻ → CrO₂OH⁻ + O=CHR

The deuterated alcohols HOCD₂R oxidize about six times slower than the undeuterated derivatives. This large kinetic isotope effect shows that the C–H (or C–D) bond breaks in the rate-determining step.

The reaction stoichiometry implicates the Cr(IV) species "CrO₂OH⁻", which comproportionates with the chromic acid to give a Cr(V) oxide, which also functions as an oxidant for the alcohol.Oxidation in Organic Chemistry. Edited by K. B. Wiberg, Academic Press, NY, 1965.

The oxidation of the aldehydes is proposed to proceed via the formation of hemiacetal-like intermediates, which arise from the addition of the O₃CrO-H⁻ bond across the C=O bond.

The reagent rarely oxidizes unsaturated bonds. In certain cases, depending on very

exact stereoelectronic factors, production of epoxides may occur.

It remains useful in organic synthesis.{{OrgSynth|volume= 45|pages = 28|year = 1965|title = Cyclooctanone|first1= E. J.|last1= Eisenbraun|doi= 10.15227/orgsyn.045.0028}}{{OrgSynth|volume= 45|page= 77|year = 1965|title = Nortricyclanone|first1=J.|last1=Meinwald|first2=J. |last2=Crandall|first3=W. E.|last3=Hymans|doi= 10.15227/orgsyn.045.0077}} A variety of spectroscopic techniques, including infrared spectroscopy, can be used to monitor the progress of a Jones oxidation reaction. At one time the Jones oxidation was used in breathalyzers.

{{main|Oxidation with chromium(VI) complexes}}

The other principal alcohol oxidation processes utilize Collins reagent, Cornforth reagent, and PCC. Many of these reagents represent improvements over inorganic chromium(VI) reagents such as Jones reagent with respect to selectivity, specifically in increased favorablility of oxidizing primary alcohols to aldehydes over carboxylic acids.{{cite journal |journal=Tetrahedron Letters|volume= 46| issue=10|page= 1651-1653|year = 2005|title = Pyridinium chlorochromate catalyzed oxidation of alcohols to aldehydes and ketones with periodic acid|first1=M.|last1=Hunsen|doi= 10.1016/j.tetlet.2005.01.076}}

• {{cite journal|author1=Bowden, K. |author2=Heilbron, I. M. |author3=Jones, E. R. H |journal = J. Chem. Soc.|year = 1946|pages = 39|doi = 10.1039/jr9460000039|title = 13. Researches on acetylenic compounds. Part I. The preparation of acetylenic ketones by oxidation of acetylenic carbinols and glycols}}
• {{cite journal|author1=Heilbron, I.M. |author2=Jones, E.R.H. |author3=Sondheimer, F |journal = J. Chem. Soc.|year = 1949|pages = 604|doi = 10.1039/jr9490000604|title = 129. Researches on acetylenic compounds. Part XV. The oxidation of primary acetylenic carbinols and glycols}}
• {{cite journal|author = Bladon, P|journal = J. Chem. Soc.|year = 1951|pages = 2402|doi = 10.1039/jr9510002402|title = 532. Studies in the sterol group. Part LII. Infra-red absorption of nuclear tri- and tetra-substituted ethylenic centres|last2 = Fabian|first2 = Joyce M.|last3 = Henbest|first3 = H. B.|last4 = Koch|first4 = H. P.|last5 = Wood|first5 = Geoffrey W.}}
• {{cite journal|author = Jones, E. R. H|journal = J. Chem. Soc.|year = 1953|pages = 457|doi = 10.1039/jr9530000457|title = 92. The chemistry of the triterpenes. Part XIII. The further characterisation of polyporenic acid A}}
• {{cite journal|author = Jones, E. R. H|journal = J. Chem. Soc.|year = 1953|pages = 2548|doi = 10.1039/jr9530002548|title = 520. The chemistry of the triterpenes and related compounds. Part XVIII. Elucidation of the structure of polyporenic acid C}}
• {{cite journal|author = Jones, E. R. H|journal = J. Chem. Soc.|year = 1953|pages = 3019|doi = 10.1039/jr9530003019|title = 599. The chemistry of the triterpenes and related compounds. Part XIX. Further evidence concerning the structure of polyporenic acid A}}
• {{cite journal|author = C. Djerassi, R. Engle and A. Bowers|title = Notes – The Direct Conversion of Steroidal Δ5-3β-Alcohols to Δ5- and Δ4-3-Ketones|year = 1956|journal = J. Org. Chem.|volume = 21|issue = 12|pages = 1547–1549|doi = 10.1021/jo01118a627}}

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Category:Organic oxidation reactions

Category:Name reactions