Methyl isobutyl ketone from acetone

A Catalytic Distillation Process for the One Step Synthesis of Methyl Isobutyl Ketone from Acetone Liquid Phase Kinetics of the Hydrogenation of Mesityl Oxide... 

Both uncalcined and calcined LDHs have also been shown to be effective supports for noble metal catalysts [18-25]. For example, palladium supported on Cu/Mg/Al LDHs has been used in the liquid phase oxidation of limonene [24], and on calcined Mg/Al LDHs for the one-pot synthesis of 4-methyl-2-pentanone (methyl isobutyl ketone) from acetone and hydrogen at atmospheric pressure [25]. In the latter case, the performance depends on the interplay between the acid-base and hydrogenation properties. More recently. 

In fact, diketones in a medium sized ring give several transannular reactions such as pinacol coupling [equation (i)] or aldolization [equation The later reaction also occurs during hydrogenation of aliphatic monoketones under favorable conditions (Pd-on-carbon, zeolite, 200°C, 4 X 10 kPa) to produce methyl isobutyl ketone from acetone (in 96%) -... 

Gandia, LM Malm, R Marchand, R Conanec, R Laurent, Y Montes, M. Application of a new hydrogenated aluminophosphate oxynitride (AlPON) as a catalytic support for the one-step synthesis of methyl isobutyl ketone from acetone. Applied Catalysis A General, 1994 114, LI-L7. 

Methyl Isobutyl Ketone. Methyl isobutyl ketone (MIBK) (4-methyl-2-pentanone), (CH2)2CHCH2COCH2, is an industrially important solvent which after methyl methacrylate and bisphenol A is the third largest tonnage product obtained from acetone. 

Acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, ethyl acetate, and tetrahydrofuran are solvents for vinyhdene chloride polymers used in lacquer coatings methyl ethyl ketone and tetrahydrofuran are most extensively employed. Toluene is used as a diluent for either. Lacquers prepared at 10—20 wt % polymer sohds in a solvent blend of two parts ketone and one part toluene have a viscosity of 20—1000 mPa-s (=cP). Lacquers can be prepared from polymers of very high vinyhdene chloride content in tetrahydrofuran—toluene mixtures and stored at room temperature. Methyl ethyl ketone lacquers must be prepared and maintained at 60—70°C or the lacquer forms a sohd gel. It is critical in the manufacture of polymers for a lacquer apphcation to maintain a fairly narrow compositional distribution in the polymer to achieve good dissolution properties. 

Other modifications of the polyamines include limited addition of alkylene oxide to yield the corresponding hydroxyalkyl derivatives (225) and cyanoethylation of DETA or TETA, usuaHy by reaction with acrylonitrile [107-13-1/, to give derivatives providing longer pot Hfe and better wetting of glass (226). Also included are ketimines, made by the reaction of EDA with acetone for example. These derivatives can also be hydrogenated, as in the case of the equimolar adducts of DETA and methyl isobutyl ketone [108-10-1] or methyl isoamyl ketone [110-12-3] (221 or used as is to provide moisture cure performance. Mannich bases prepared from a phenol, formaldehyde and a polyamine are also used, such as the hardener prepared from cresol, DETA, and formaldehyde (228). Other modifications of polyamines for use as epoxy hardeners include reaction with aldehydes (229), epoxidized fatty nitriles (230), aromatic monoisocyanates (231), or propylene sulfide [1072-43-1] (232). 

After the end of the fermentation (28 hours) the culture broth is filtered off by suction over a large suction filter. The mycel residue is washed with water several times. The filtrate is extracted three times, each time with 10 liters of methyl isobutyl ketone. The extract is concentrated under vacuum in a circulating evaporator and in a round flask carefully dried under vacuum. The residue is crystallized from acetone/isopropyl ether. The melting point is 157°-158°C (fermentation yield = 60%). The pure product yield obtained after a second crystallization and chromatography of the mother liquor on silica gel amounts to 53% of the theoretical. 

In this study we examine the generalities in reductive alkylation however, since the subject is vast, we limited ourselves to the interaction of aromatic and aliphatic primary amines and diamines with ketones. The ketones examined include the cyclic ketone, cyclohexanone, and aliphatic ketones such as acetone, and methyl isobutyl ketone (MIBK). We limited our study to sulfided and unsulfided Pt and Pd catalysts supported on activated carbon that were commercially available from Evonik Degussa Corporation. 

It is clear that kinetic effects must be utilized in the design of a process to make the commercially available Form A, because it is never the most thermodynamically stable form. Information from the literature and patents in reference [14] indicates that Form A can be successfully isolated from Acetonitrile, Acetone, Methyl isobutyl ketone, Toluene, the C2 to C4 alkenols, Ethanol, Methanol and Propan-2-ol. In these solvents it is likely that solvation is favourable to the nucleation rate of Form A or detrimental to crystal growth of the other forms, or both. For a new development compound there should be similar solvent interaction data available from polymorph screening experiments. 

Figure 12.8 S3fnthesis of methyl isobutyl ketone (MIBK) from acetone.

Aldol chemicals refer to a variety of substances desired from acetone involving an aldol condensation in a portion of their synthesis. The most important of these chemicals is methyl isobutyl ketone (MIBK), a common solvent for many coatings, pesticides, adhesives, and pharmaceuticals. Approximately 0.17 billion lb of MIBK were made in recent years. The synthesis is outlined on the next page. 

Chemicals and Standard Solutions. Cyclohexanone, cyclohexanol, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, phenol, 4-methylphenol, 4-chloro-phenol, 1,2,3,4-tetrahydroisoquinoline, 1-chlorohexane, 1-chlorododecane, and 1-chlorooctadecane were obtained from Aldrich. Acetone, tetrahydrofuran, ethyl acetate, toluene, dimethyl sulfoxide, and methanol were obtained from J. T. Baker. Distilled-in-glass isooctane, methylene chloride, ethyl ether, and pentane were obtained from Burdick and Jackson. Analytical standard kits from Analabs provided methyl ethyl ketone, isopropyl alcohol, ethanol, methyl isobutyl ketone, tetrachloroethylene, dodecane, dimethylformamide, 1,2-dichlorobenzene, 1-octanol, nitrobenzene, 2,4-dichlorophenol, and 2,5-dichlorophenol. All chemicals obtained from the vendors were of the highest purity available and were used without further purification. High-purity water... 

Compound recovery data for duplicate runs differed by 2-15, depending on the compound. Half-normal probability plot analysis of the new data for the anomalous compounds indicated none of the distortion encountered earlier. Results for acetone and tetrachloroethylene now indicated only random variation with no significant outliers. Results for 2,4-dichlorophenol and 2,5-dichlorophenol indicated a significant pH effect. A significant interaction effect (AB) was detected between variables pH and primary column type for the dichlorophenols and also for methyl isobutyl ketone. This interaction effect indicates that at approximately low pH (pH 2), compound recoveries for dichlorophenols will be greater when a C18 phase is used as the primary column. The half-normal plot for 2,5-dichlorophenol is shown in Figure 10. In examining data for all the compounds from the 23 replicate factorials, this interaction consistently appears for phenolic compounds. 

Major markets as solvents and intermediates have made the ketones important commercial products lor many years. Acetone and mcthylethyl ketone have had the most impact on the chemical industry Acetone Is used s an intermediate In methyl isobutyl ketone, methyl methacrylate, diucelonc alcohol. ketone. hisphenol-A. phiwnc. and mesityl oxide Acetone is largely produced by dehydration of isopropyl alcohol In the production of phenol from cumene, acetone is produced as a by-product This mute to acetone has tended to control its price. 

A widely studied example of this kind is the synthesis of methyl isobutyl ketone (MIBK, used as a solvent for inks and lacquers) from acetone. The former was previously prepared from the latter through a catalytic three-step process base-catalysed production of 4-hydroxy-4-methylpentan-2-one, acid dehydration into mesityloxide (MO), then hydrogenation of MO on a Pd catalyst. Since acetone aldolization occurs through acid catalysis as shown over a H-MFI zeolite at 433 K (MO is the main reaction product, the aldolization product being rapidly dehy-drated[5]), it is possible, by associating with the acid catalyst a hydrogenation phase,... 

Epoxyglycerides react with ketones in the presence of boron trifluoride to give 1,3-dioxolane derivatives. In this form they were analysed by GC on a column packed with 3% of OV-1 with temperature programming at 4°C/min from 260° C [649]. Cyclo-pentanone was recommended as the most suitable reagent, and acetone, methyl ethyl ketone, methyl isobutyl ketone and others can also be used. 

Clearing doses were determined by immersing the wafers in a strong solvent (acetone) for two minutes. Standard dip development was carried out by immersion in MIBK (methyl-isobutyl-ketone) at 21°C for time increments from one minute to ten minutes. The dissolution rate was calculated from thickness loss, measured using a Nanospec, and development time. SEM examination of test structures was used to evaluate the resolution of the resist under the different processing conditions. Unless specifically mentioned, each experiment showed that 0.5ym features could be resolved in the resist. 

A mixture containing 50.0 wt% acetone and 50.0 wt% water is to be separated into two streams— one enriched in acetone, the other in water. The separation process consists of extraction of the acetone from the water into methyl isobutyl ketone (MIBK), which dissolves acetone but is nearly immiscible with water. The description that follows introduces some of the terms commonly used in reference to liquid extraction processes. The process is shown schematically below. 

Figure 6.6-1 Triangular phase diagram for water-acetone-methyl isobutyl ketone (composition in wt%) at 25°C (From D. F. Othmer, R. E. White, and E.

Enones are reduced to saturated ketones by catalytic hydrogenation provided the reaction is stopped following the absorption of 1 mol of hydrogen. " A number of catalysts were found useful for this, including platinum, platinum oxide,Pt/C, " Pd/C, - Rh/C, " tris(triphenylphosphine)rhodium chloride, - nickel-aluminum alloy in 10% aqueous NaOH, and zinc-reduced nickel in an aqueous medium. Mesityl oxide is formed from acetone and reduced in a single pot to methyl isobutyl ketone using a bifunctional catalyst which comprised palladium and zirconium phosphate (Scheme 20). 

Organic solvents have long been used for extraction and sequential extraction, which is fractionation of a sort (Flaig et al., 1975 Schnitzer, 1978). While the direct use of organic solvents in fractionation has not been widespread, nonetheless, the technique has received some attention. For instance, the separation of hymatomelanic acid from precipitated humic acid is obtained by extraction with ethanol (Oden, 1919). Ethanol has been used to bring about fractional precipitation by addition to alkaline solutions of humic acid (Kyuma, 1964 Kumada and Kawamura, 1968). There is no reason why other water-miscible solvents such as acetone and methanol should not be used in this way. Solvents that are highly immiscible with water (e.g., hexane and benzene) do not appear to remove any substantial fraction of humic substances. These are perhaps best used to remove nonhumic substances (such as fats and waxes) prior to extraction. However, recent work by Allen and MacCarthy (personal communication) has shown that more polar water-immiscible solvents, such as methyl isobutyl ketone and diethyl ether, can be used successfully to purify and fractionate humic substances. 

Example 203. A countercurrent extraction plant is used to extract acetone A) from its mixture with water by means of methyl isobutyl ketone (MIK) at a temperature of 25°C. The feed consists of 40 percent acetone and 60 percent water. Pure solvent equal in mass to the feed is used as the extracting liquid. How many ideal stages are required to extract 99 percent of the acetone fed What is the extract composition after removal of the solvent ... 

Liquid-Liquid Extraction of an Organic Chemical from Aqueous Solution It is desired to remove some of the acetone from a mixture that contains 60 wt % acetone and 40 Wt % water by extraction with methyl isobutyl ketone (MIK). If 3 kg of MIK are contacted with 1 kg of the acetone-water mixture, what will be the amounts and compositions of the equilibrium phases ... 

By this single liquid-liquid extraction step we have been able to remove most of the acetone from the water. However, a great deal of methyl isobutyl ketone has been used. Consequently, this would not be a very useful way to. recover acetone from aqueous solution. To reduce the amount... 

Crystals from 20% ale or ether, rap 140° (conflagrates). Stable in air for about one day after which the crystals turn black and become insol in ether. Sol in ale, acetone, ether, chloroform, methyl isobutyl ketone slightly sol in water practically insol in hexane. Absorption spectrum Ash-... 

Brilliant yellow needles from n-hutanol, dec 273-276. Sublimes 2OOV0.1 mm. uv max (methanol) 250, 311 388 nm (e 6300, 5700, 11,000) (Celmer Solomons). Sparingly sol in water (210 mg/l) more sol in methanol ethanol chloroform, acetone (1% soins in acetone have been prepd) glacial acetic acid, methyl isobutyl ketone. Less sol in ether, benzene, hexane. Stable in acid and neutral solns dec in alkaline solo Effective vs gram -positive and gram -negative becteria fungi and ameboid parasites. LD9 in mice (mg/kg) 5-10 s.c. 10 Orally LD in mice (mg/kg) 25 s.c. 25 orally (Seneca). 

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