Acetone, oxidation

Dimethyl dioxirane in wet acetone oxidizes isocyanates to nitro compounds (RNCO —> RN02). Oximes can be oxidized to nitro compounds with peroxytri-fluoroacetic acid, or Oxone ," sodiumperborate," among other ways. " Primary and secondary alkyl azides have been converted to nitro compounds by treatment with PhjP followed by ozone. Aromatic nitroso compounds are easily oxidized to nitro compounds by many oxidizing agents. ... 

The rapid oxidations of certain of these polyfunctional compounds by alkaline permanganate were examined as a supplement to the study of acetone oxidation (p. 314). The oxidations of acetol and pyruvaldehyde show identical rate laws of the form... 

Janssen PH, B Schink (1995a) Metabolic pathways and energetics of the acetone-oxidizing sulfate-reducing bacterium Desulfobacterium cetonicum. Arch Microbiol 163 188-194. 

Acetone was accidentally introduced into a reactor containing a sulphuric acid/nitric acid/hydrogen peroxide mixture. This led to an explosion due to acetone oxidation by the peroxymonosulphuric acid formed by the oxidising mixture. 

Two syntheses of hernandaline (197) have been carried out. Dutschewska and Mollov (162) prepared it by potassium permanganate in acetone oxidation of thalmelatine (201), while Cava et al. (158) performed the synthesis... 

Solvents Water (purified water or water-for-injection grade) toluene, methanol, ethanol, ether, acetate, dimethyl sulfoxide, tetrahydrofuran, hexane, cyclohexane, dichloromethane, acetonitrile, acetone Oxidizing Agents Hydrogen peroxide, chromic acid, potassium permanganate, manganese dioxide, ozone... 

A detailed study271 on the reaction of 2,3-dimethyl-2-butene with ozone revealed that epoxide formation strongly depends on alkene concentration and temperature. Under appropiate reaction conditions (neat alkene, 0°C) the corresponding tetra-methyloxirane was the main product. Dimethyldioxirane formed from energy-rich acetone oxide (a cleavage product of the alkene) was postulated to be responsible for epoxidation. 

The Reichstein-Griissner process, developed in 1934, takes in all five chemical steps (hydrogenation, fermentative oxidation, acetonization, oxidation, and hydroly-sis/rearrangement) (Table 20.3). Over the course of the whole synthesis there are 17-20 different downstream processing steps, six solid-handling steps, and at least seven different solvent systems to handle. The overall yield is about 55%, and overall cycle time is around three days. Such values clearly suggest possible improvement in the process towards ascorbic acid. 

Reactions involving abstraction from acetaldehyde are just as likely in diethyl ketone oxidation as reactions involving abstraction from formaldehyde in acetone oxidation. The acetyl radical so produced will oxidize as in the oxidation of acetone to give mostly carbon dioxide (from the -carbon atom of diethyl ketone71), but a little decomposition seems to occur since some carbon monoxide does not come from the original carbonyl group of the ketone.71... 

Although [Re2(NCS)s] forms from substitution of [Re2CU] with thiocyanate in acidic MeOH, when [SCN] is added to [Re2Cl8] in acetone oxidation to [RefNCS) ] and [Re2(NCS)io] occurs. The mixed-valence Refill, IV) dimer has a conlateral bioctahedral geometry with two N-bridging thiocyanate ligands and an Re-Re distance of 261 pm. 

Properties Yellow powder. D 5.117 (17C), bp 619C, mp 215C. Soluble in hydrochloric acid (dilute) soluble in water, alcohol, ether, and acetone oxidizes and turns brown in air. 

C. Reed, Y. Xi, S. T. Oyama, Distinguishing between reaction intermediates and spectators A kinetic study of acetone oxidation using ozone on a silica-supported manganese oxide catalyst, J. Catal. 235 (2005) 378. 

Catalytic performance in the complete acetone oxidation of manganese and cobalt oxides supported on alumina and silica... 

Recently, the 4-methyl ethers of (90A) and (91A), methyl 4-0-methyl-d-D-ara ino-hexopyranosidulose and methyl 4-0-methyl- 8-D-ri6o-hexo-pyranosid-3-ulose, respectively, have also been prepared by using chromium trioxide/acetone oxidation. The latter, which was preponderant, was obtained crystalline. 

Metal acetyl acetonate Oxidation-reduction potential (u) Catalytic activitya... 

Jones ox. CrOi/HjSOacetone oxidant sepn. separation... 

A-Bromosuccinimide or KMn04 in acetone oxidizes 4,5-dihydroisoxazoles to give isoxazoles. 

CAN-mediated nitration provides a convenient route for the introduction of a nitro group into a variety of substrates. Alkenes on treatment with an excess of sodium nitrite and CAN in chloroform under sonication afford nitroalkenes. When acetonitrile is used as the solvent, nitroacetamidation occurs in a Ritter-type fashion. However, the attempted nitroacetamidation of cyclo-pentene-1 -carboxaldehyde under similar conditions resulted in the formation of an unexpected dinitro-oxime compound. A one-pot synthesis of 3-acetyl- or 3-benzoylisoxazole derivatives by reaction of alkenes (or alkynes) with CAN in acetone or acetophenone has been reported. The proposed mechanism involves a-nitration of the solvent acetone, oxidation to generate the nitrile oxide, and subsequent 1,3-dipolar cycloaddition with alkenes or alkynes. The nitration of aromatic compounds such as carbozole, naphthalene, and coumarins by CAN has also been investigated. As an example, coumarin on treatment with 1 equiv of CAN in acetic acid gives 6-nitrocoumarin in 92% yield. ... 

Pyridine is efficiently converted to its tV-oxide by the Oxone-acetone oxidant. Cytosine and several of its derivatives give the A 3-oxides selectively upon reaction with buffered Oxone (eq 17). A similar transformation of adenosine 5 -monophosphate yields the Al-oxide. ... 

Boron, Phosphorus, and Selenium Compounds. Oxone has been used to oxidize carbon-boron bonds during the work-up of hydroboration reactions to obtain high yields of the resultant alcohols (eq 73). Aqueous Oxone/acetone oxidizes electron-poor and electron-rich aromatic and aliphatic boronic acids and esters to the corresponding alcohols rapidly and efficiently (eq 74). A one-pot procedure for the synthesis of iweta-substituted phenols from benzenes has been developed, and a similar strategy has been devised for the synthesis of Boc-oxindoles from Boc-indoles. i3i... 

Experiment 19.5 Catalysis of acetone oxidation by copper. A copper spiral is heated by a laboratory gas burner until all coils glow red. It is then positioned closely over the surface of acetone in a beaker. The processes taking place upon the surface can be seen by the periodic glowing of parts of the spiral. There is also the typical stinging smell of aldehyde. 

In conclusion, on anatase, photo-oxidation of acetone limits the total oxidation, whereas on rutile, formate does so. The latter is attributed to a combination of thermal dissociation of acetone on defect sites, which aids acetone oxidation, and the strong bonding of p-formate to the (110) surface facets on rutile. A synergetic effect between anatase and rutile particles is observed, where the measured photooxidation rate from either quadrupole mass spectrometry (QMS) or DRIFTS exceeds than that for the individual constituent particles. 

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