Mesityl oxide

Synonyms 3-pentanone propione dimethyl acetone methacetone pentan-3-one 

Diethyl ketone is nsed as a solvent, in medicine, and in organic synthesis. 

Colorless liquid with a characteristic pungent odor bp 101.7°C (215.06°F) mp -39.8°C (-39.64°F) density 0.814 at 20°C (68°F) soluble in alcohol and acetone, slightly soluble in water. 

Diethyl ketone is a mild narcotic compound as well as an irritant. Its acute toxicity is less than that of methyl propyl ketone. Exposure to 80,000 ppm for 4 hours was fatal to rats. 

Flammable liquid flash point (open cnp) 13°C (55°F) vapor density 3 (air = 1) the vapor can travel some distance to an ignition sonrce and flashback antoignition tempera-tnre 450°C (842°F) fire-extinguishing agent alcohol foam a water spray can be nsed to flnsh and dilnte the spill. Diethyl ketone forms explosive mixtnres with air the FEE valne is 1.6% by volnme of air, the UEL valne is not reported. 

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Assemble a 250 ml. three-necked flask, fitted with a stirrer, a reflux condenser and a dropping-funnel, as in Fig. 22(A) and (j), p. 43, or Fig. 23(c), p. 46 (or a two-necked flask, with the funnel fitted by a grooved cork (p. 255) to the top of the condenser). Place 40 ml. of ethanol in the flask, and then add 2-3 g. of sodium cut into small pieces. When all the sodium has dissolved, heat the stirred solution on the water-bath, and run in from the funnel 17 g. (17 ml.) of ethyl malonate and then (more slowly) io-2 g. (12 ml.) of mesityl oxide, the reaction-mixture meanwhile forming a thick slurry. Boil the stirred mixture under reflux for i hour, and then add a solution of 10 g. of sodium hydroxide in 50 ml. of water, and continue boiling the pale honey-coloured solution for ij hours more. 

The residual liquid contains about 95 per cent, of diacetone alcohol and is satisfactory for the preparation of mesityl oxide (Section 111,79). 

The product, an ap unaaturated ketone, is known as mesityl oxide. 

Fit a 750 ml. round-bottomed flask with a fractionating column attached to a condenser set for downward distillation. Place 500 g. of diacetone alcohol (the crude product is quite satisfactory), 01 g. of iodine and a few fragments of porous porcelain in the flask. Distil slowly. with a small free flame (best in an air bath) and collect the following fractions (a) 56-80° (acetone and a little mesityl oxide) (6) 80-126° (two layers, water and mesityl oxide) and (c) 126-131° (mesityl oxide). Whilst fraction (c) is distilling, separate the water from fraction (6), dry with anhydrous potassium carbonate or anhydrous magnesium sulphate, and fractionate from a small flask collect the mesityl oxide at 126-131°. The yield is about 400 g. 

Fit a 1-litre three-necked flask with two double surface condensers and a glycerine-scaled stirrer (Fig. II, 7, 10). Place 25 g. (29 ml.) of mesityl oxide (Section 111,79), 50 ml. of dioxan and a cold (10°) solution... 

It la of Interest to note that the preparation of dimethyldihydroresorcinol (also named dlmedone and methone Section VII, 15) involves an initial Dchael addition to mesityl oxide, followed by an internal Claiaen condensation. 

Mesityl oxide (Section 111,79) (I) condenses with ethyl malonate in the presence of sodium ethoxide to give the sodium derivative of (II) this upon hydrolysis with aqueous potassium hydroxide, followed by acidification, gives the cyclic diketone 5 5-dimethyl-l 3-cycfohexanedione (III), of which the enoUc form is 5 5-dimethyldihydroresorcinol (IV) ... 

Various 4-, 5-, or 4,5-disubstituted 2-aryIamino thiazoles (124), R, = QH4R with R = 0-, m-, or p-Me, HO C, Cl, Br, H N, NHAc, NR2, OH, OR, or OjN, were obtained by condensing the corresponding N-arylthiourea with chloroacetone (81, 86, 423), dichloroacetone (510, 618), phenacyichloride or its p-substituted methyl, f-butyl, n-dodecyl or undecyl (653), or 2-chlorocyclohexanone (653) (Method A) or with 2-butanone (423), acetophenone or its p-substituted derivatives (399, 439), ethyl acetate (400), ethyl acetyl propionate (621), a- or 3-unsaturated ketones (691), benzylidene acetone, furfurylidene acetone, and mesityl oxide in the presence of Btj or Ij as condensing agent (Method B) (Table 11-17). 

Commercial mesityl oxide (CH3)2C=CHCCH3 is often contam mated with about 10% of an isomer having the same carbon skeleton What is a Jikely structure for this compound ... 

Mesityl oxide 2-Aminoethanol, chlorosulfonic acid, nitric acid, ethylenediamine, sulfuric acid... 

Furfural reacts with ketones to form strong, crosslinked resins of technical interest in the former Soviet Union the U.S. Air Force has also shown some interest (42,43). The so-called furfurylidene acetone monomer, a mixture of 2-furfurylidene methyl ketone [623-15-4] (1 )> bis-(2-furfurylidene) ketone [886-77-1] (14), mesityl oxide, and other oligomers, is obtained by condensation of furfural and acetone under basic conditions (44,45). Treatment of the "monomer" with an acidic catalyst leads initially to polymer of low molecular weight and ultimately to cross-linked, black, insoluble, heat-resistant resin (46). 

Primary amines form Schiff bases, (CH3 )2C=NR. Ammonia induces an aldol condensation followed by 1,4-addition of ammonia to produce diacetone amine (from mesityl oxide), 4-amino-4-methyl-2-pentanone [625-04-7] (CH2)2C(NH2)CH2COCH2, and triacetone amine (from phorone),... 

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). 

Although the selectivity of isopropyl alcohol to acetone via vapor-phase dehydrogenation is high, there are a number of by-products that must be removed from the acetone. The hot reactor effluent contains acetone, unconverted isopropyl alcohol, and hydrogen, and may also contain propylene, polypropylene, mesityl oxide, diisopropyl ether, acetaldehyde, propionaldehyde, and many other hydrocarbons and carbon oxides (25,28). 

Some unsaturated ketones derived from acetone can undergo base- or acid-catalyzed exothermic thermal decomposition at temperatures under 200°C. Experiments conducted under adiabatic conditions (2) indicate that mesityl oxide decomposes at 96°C in the presence of 5 wt % of aqueous sodium hydroxide (20%), and that phorone undergoes decomposition at 180°C in the presence of 1000 ppm iron. The decomposition products from these reactions are endothermic hydrolysis and cleavage back to acetone, and exothermic aldol reactions to heavy residues. 

In the three-step process acetone first undergoes a Uquid-phase alkah-cataly2ed condensation to form diacetone alcohol. Many alkaU metal oxides, metal hydroxides (eg, sodium, barium, potassium, magnesium, and lanthanium), and anion-exchange resins are described in the Uterature as suitable catalysts. The selectivity to diacetone alcohol is typicaUy 90—95 wt % (64). In the second step diacetone alcohol is dehydrated to mesityl oxide over an acid catalyst such as phosphoric or sulfuric acid. The reaction takes place at 95—130°C and selectivity to mesityl oxide is 80—85 wt % (64). A one-step conversion of acetone to mesityl oxide is also possible. 

Finally, selective hydrogenation of the olefinic bond in mesityl oxide is conducted over a fixed-bed catalyst in either the Hquid or vapor phase. In the hquid phase the reaction takes place at 150°C and 0.69 MPa, in the vapor phase the reaction can be conducted at atmospheric pressure and temperatures of 150—170°C. The reaction is highly exothermic and yields 8.37 kJ/mol (65). To prevent temperature mnaways and obtain high selectivity, the conversion per pass is limited in the Hquid phase, and in the vapor phase inert gases often are used to dilute the reactants. The catalysts employed in both vapor- and Hquid-phase processes include nickel (66—76), palladium (77—79), copper (80,81), and rhodium hydride complexes (82). Complete conversion of mesityl oxide can be obtained at selectivities of 95—98%. 

Figure 2 illustrates the three-step MIBK process employed by Hibernia Scholven (83). This process is designed to permit the intermediate recovery of refined diacetone alcohol and mesityl oxide. In the first step acetone and dilute sodium hydroxide are fed continuously to a reactor at low temperature and with a reactor residence time of approximately one hour. The product is then stabilized with phosphoric acid and stripped of unreacted acetone to yield a cmde diacetone alcohol stream. More phosphoric acid is then added, and the diacetone alcohol dehydrated to mesityl oxide in a distillation column. Mesityl oxide is recovered overhead in this column and fed to a further distillation column where residual acetone is removed and recycled to yield a tails stream containing 98—99% mesityl oxide. The mesityl oxide is then hydrogenated to MIBK in a reactive distillation conducted at atmospheric pressure and 110°C. Simultaneous hydrogenation and rectification are achieved in a column fitted with a palladium catalyst bed, and yields of mesityl oxide to MIBK exceeding 96% are obtained. 

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