Acetone from oxidation

This oxidation process for olefins has been exploited commercially principally for the production of acetaldehyde, but the reaction can also be apphed to the production of acetone from propylene and methyl ethyl ketone [78-93-3] from butenes (87,88). Careflil control of the potential of the catalyst with the oxygen stream in the regenerator minimises the formation of chloroketones (94). Vinyl acetate can also be produced commercially by a variation of this reaction (96,97). 

The yield of acetone from the cumene/phenol process is beUeved to average 94%. By-products include significant amounts of a-methylstyrene [98-83-9] and acetophenone [98-86-2] as well as small amounts of hydroxyacetone [116-09-6] and mesityl oxide [141-79-7]. By-product yields vary with the producer. The a-methylstyrene may be hydrogenated to cumene for recycle or recovered for monomer use. Yields of phenol and acetone decline by 3.5—5.5% when the a-methylstyrene is not recycled (21). 

Another method of manufacture involves the oxidation of 2-isopropylnaphthalene ia the presence of a few percent of 2-isopropylnaphthalene hydroperoxide/i)ti< 2-22-(y as the initiator, some alkaU, and perhaps a transition-metal catalyst, with oxygen or air at ca 90—100°C, to ca 20—40% conversion to the hydroperoxide the oxidation product is cleaved, using a small amount of ca 50 wt % sulfuric acid as the catalyst at ca 60°C to give 2-naphthalenol and acetone in high yield (70). The yields of both 2-naphthalenol and acetone from the hydroperoxide are 90% or better. 

Other by-products include acetone, carbonaceous material, and polymers of propylene. Minor contaminants arise from impurities in the feed. Ethylene and butylenes can form traces of ethyl alcohol and 2-butanol. Small amounts of / -propyl alcohol carried through into the refined isopropyl alcohol can originate from cyclopropane [75-19-4] in the propylene feed. Acetone, an oxidation product, also forms from thermal decomposition of the intermediate sulfate esters, eg. 

Production of a-methylstyrene (AMS) from cumene by dehydrogenation was practiced commercially by Dow until 1977. It is now produced as a by-product in the production of phenol and acetone from cumene. Cumene is manufactured by alkylation of benzene with propylene. In the phenol—acetone process, cumene is oxidized in the Hquid phase thermally to cumene hydroperoxide. The hydroperoxide is spHt into phenol and acetone by a cleavage reaction catalyzed by sulfur dioxide. Up to 2% of the cumene is converted to a-methylstyrene. Phenol and acetone are large-volume chemicals and the supply of the by-product a-methylstyrene is weU in excess of its demand. Producers are forced to hydrogenate it back to cumene for recycle to the phenol—acetone plant. Estimated plant capacities of the U.S. producers of a-methylstyrene are Hsted in Table 13 (80). 

A direct route for acetone from propylene was developed using a homogeneous catalyst similar to Wacker system (PdCl2/CuCl2). The reaction conditions are similar to those used for ethylene oxidation to acetaldehyde. ... 

A useful way of classifying chemicals is shown in Fig. 2.1. Chemicals are divided on the basis of volume and character. Bulk chemicals, or commodities, are produced in large quantities and sold on the basis of an industry specification. There is essentially no difference in the product from different suppliers. Typical examples would be acetone, ethylene oxide, and phenol. Pseudo commodities are also made in large quantities but are sold on the basis of their performance. In many cases the product is formulated and properties can differ from one supplier to another. Examples include large volume polymers, surfactants, paints, etc. 

In the absence of other ignition source), fires in plant to recover acetone from air with active carbon are due to the bulk surface effect of oxidative heating when air flow is too low to cool effectively. 

The diselenides [A -(6-Et-4-pyrimidone)(6-Et-SeU)J (31) and [7V-(6-n-Pr-4-pyrimidone)(6-n-Pr-SeU)j] (32) were produced upon re-ciystallization of [( -PrSeU)IJ (30) and [(n-EtSeU) ] (33) from acetone, as oxidation products. On the other hand deselenation with the formation of 6-n-propyl-2-uracil (n-Pr-U) (34) was observed when (30) was re-crystallized from methanol/acetonitrile solutions [7]. 

Autoxidation. Self-catalyzed oxidation in the presence of air. Autoxidation can be initiated by heat, light, or a catalyst. The commercial production of phenol and acetone from cumene is autoxidation. Other examples include the degradation of polymers exposed to sunlight for long periods of time gum formation in lubricating oils and gasoline and the spoilage of fats. 

The earliest paper in this field used RuO from RuO /aq. Na(10 )/AcOH for cleavage of 4-cholesten-3-one and hexahydroindene to the corresponding carboxylic acids (Fig. 1.5) [195] minimal experimental data were given. An early example (1959) for RuOj/aq. Na(IO )/acetone involved oxidation of 3a-acetoxy-24,24-di-phenylchol-23-ene to 3a-acetoxynorcholanic acid [196],... 

Kennedy and Stock reported the first use of Oxone for many common oxidation reactions such as formation of benzoic acid from toluene and of benzaldehyde, of ben-zophenone from diphenyhnethane, of frawi-cyclohexanediol Ifom cyclohexene, of acetone from 2-propanol, of hydroquinone from phenol, of e-caprolactone from cyclohexanone, of pyrocatechol from salicylaldehyde, of p-dinitrosobenzene from p-phenylenediamine, of phenylacetic acid from 2-phenethylamine, of dodecylsulfonic acid from dodecyl mercaptan, of diphenyl sulfone from diphenyl sulfide, of triphenylphosphine oxide from triphenylphosphine, of iodoxy benzene from iodobenzene, of benzyl chloride from toluene using NaCl and Oxone and bromination of 2-octene using KBr and Oxone . Thus, they... 

Alkenes are directly oxidized to aldehydes and/or ketones by ozone (O3) at low temperatures (—78 °C) in methylene chloride, followed by the reductive work-up. For example, 2-methyl-2-butene reacts with O3, followed by a reductive work-up to yield acetone and acetaldehyde. This reducing agent prevents aldehyde from oxidation to carboxylic acid. 

A series of novel styrene- and siloxane-based silanol polymers and copolymers were synthesized by a selective oxidation of the Si—H bond with a dimethyldioxirane solution in acetone from corresponding precursor polymers. The conversion of the Si—H to Si—OH in the polymer modification proceeded rapidly and selectively. The silanol polymers obtained in situ showed no tendency for self-condensation to form siloxane crosslinks in solution. Moreover, stable silanol polymers in the solid states were obtained by placing bulky substitute groups bonded directly to the silicon atom. It was found that the properties of these novel silanol polymers and copolymers depended largely on substituents bonded directly to the silicon atom and silanol composition in the copolymers as well. 

Polymer modification is of particular interest when the desired polymer is not readily available from its corresponding monomer by conventional polymerization methods. The primary challenge of polymer modification is to achieve a high conversion and selective modification of the appropriate functional group. In this paper, we describe a new convenient polymer modification to prepare novel silanol polymers by a rapid and selective oxidation of the Si—H bond with a dimethyldioxirane solution in acetone from their corresponding precursor polymers. 

The rather toxic methylglyoxal is formed in many organisms and within human tissues.174 It arises in part as a side reaction of triose phosphate isomerase (Eq. 13-28) and also from oxidation of acetone (Eq. 17-7) or aminoacetone, a metabolite of threonine (Chapter 24).175 In addition, yeast and some bacteria, including E. coli, have a methylglyoxal synthase that converts dihydroxyacetone to methylglyoxal, apparently using a mechanism similar to that of triose phosphate isomerase. It presumably forms enediolate 2 of Eq. 13-26, which eliminates inorganic phosphate to yield methyl-... 

Hornsey (1956) also found that extraction with an acidified 80% acetone solution for 1 hr gave a hemin solution, derived from oxidation of the heme moiety of both NO-heme and non-nitrosylated heme pigments. Hemin absorption spectra exhibited distinct peaks at 512 and 640 nm. Hornsey (1956) used the A640 of sample filtrates as a measure of the total heme pigments. Solutions of both hemin and NO-heme in 80% acetone conformed with Beer s... 

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