Methyl ethyl ketone from -butenes

Table 10.9 lists the main economic data available on the production of methyl ethyl ketone from n-butenes, in two steps involving the intermediate formation of secondary butyl alcohol by sulfuric hydration followed by dehydrogenation, or directly by the Wacker/Hoechst technology. 

Hasegawa, H. and Triuchijima, M. (1971) Process for the Production of Methyl Ethyl Ketone from n-Butene, Maruzen Oil Co. (1971) Patent GB 1.240.889. 

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). 

Methyl Isopropyl Ketone. Methyl isopropyl ketone [563-80-4] (3-methyl-2-butanone) is a colorless Hquid with a characteristic odor of lower ketones. It can be produced by hydrating isoprene over an acidic catalyst at 200—300°C (150,151) or by acid-catalyzed condensation of methyl ethyl ketone and formaldehyde to 2-methyl-l-buten-3-one, foUowed by hydrogenation to the product (152). Other patented preparations are known (155,156). Methyl isopropyl ketone is used as an intermediate in the production of pharmaceuticals and fragrances (see Perfumes), and as a solvent (157). It is domestically available from Eastman (Longview, Texas) (47). 

Methyl ethyl ketone MEK (2-butanone) is a colorless liquid similar to acetone, but its boiling point is higher (79.5°C). The production of MEK from n-butenes is a liquid-phase oxidation process similar to that used to... 

Mixed C4 olefins (primarily iC4) are isolated from a mixed C olefin and paraffin stream. Two different liquid adsorption high-purity C olefin processes exist the C4 Olex process for producing isobutylene (iCf ) and the Sorbutene process for producing butene-1. Isobutylene has been used in alcohol synthesis and the production of methyl tert-butyl ether (MTBE) and isooctane, both of which improve octane of gasoHne. Commercial 1-butene is used in the manufacture of both hnear low-density polyethylene (LLDPE) and high-density polyethylene (HDPE)., polypropylene, polybutene, butylene oxide and the C4 solvents secondary butyl alcohol (SBA) and methyl ethyl ketone (MEK). While the C4 Olex process has been commercially demonstrated, the Sorbutene process has only been demonstrated on a pilot scale. 

Butene is oxidized to methyl ethyl ketone, presumably arizing from the acid-catalyzed rearrangement of the peroxide. Alkenols and aldehydes are formed in lower amounts. Cyclopentene is more reactive towards oxidation than butenes. 

Methyl n-amyl carbinol. 247, 254 Methyl n-amyl ketone, 482 Methylaniline (mono), pure, from commercial methylaniline, 562, 570 P-Methylanthraquinone, 728, 740 Methyl benzoate, 780, 781 p-Methyl benzyl alcohol, 811,812 Methyl benzyl ketone, 727, 735 Methyl y-bromocrotonate, 926, 927 2-Methyl-2-butene, 239 Methyl n-butyl carbinol, 247,255 Methyl n-butyl ether, 314 Methyl n-butyl ketone, 475, 481 4-Methylcarbostyril, 855 p-Methylcinnamic acid, 719 4-Methylcoumarin, 853, 854 Methyl crotonate, 926, 927 Methylethylacetic acid, 354, 358 Methylethylethynyl carbinol, 468 Methyl ethyl ketone, 335, 336 purification of, 172 Methyl n-hexyl ether, 314 Methyl n-hexyl ketone, 335, 336 Methyl n-hexyl ketoxime, 348 Methyl hydrogen adipate, 938 Methyl hydrogen sebacate, 938,939 4-Methyl-7-hydroxycoumarin, 834 Methyl iodide, 287 Methyl isopropyl carbinol, 247,255 Methyl 4-keto-octanoate, 936... 

The effect of temperature on the yields of the three addition products, a-butene oxide, n-butyraldehyde, and methyl ethyl ketone, and of a fragmentation product, carbon monoxide, is shown in Figure 3. It is seen that as temperature is increased from 25-200°C. the yields of the... 

A series of Vap GC analyses on approximately 50 mg of all the aged resin samples was conducted. Ethanal, propanal, isobutyraldehyde, propenal, butenal, methyl ethyl ketone (MEK), and methyl penetenal were positively identified by mass spectrometry. With the exception of MEK, all compounds identified (the major products) were aldehydes. Methyl ethyl ketone, the solvent used in MY720, remains even after cure. The aldehydes, however, are not impurities in either the MY720 or DOS and represent compounds which are characteristic of the resin alone. These compounds are either produced during the curing process or are formed from the thermal decompositon of a labile compound which is formed during cure. 

Preparation of Monomers. Methyl vinyl ketone (MVK) was obtained from Pfizer Chemical Division, New York, and distilled to remove the inhibitor. Methyl isopropenyl ketone (MIPK) was prepared by the aldol condensation of methyl ethyl ketone and formaldehyde, according to the method of Landau and Irany 0. The major impurity in this monomer is ethyl vinyl ketone (5. The monomer was redistilled before use. 3 Ethyl 3 buten 2 one (EB) was prepared by the aldol condensation of methyl propyl ketone and formaldehyde. Ethyl vinyl ketone (EVK) was prepared by a Grignard synthesis of the alcohol, followed by oxidation to the ketone. t-Butyl vinyl ketone (tBVK) was prepared from pinacolone and formaldehyde by the method of Cologne (9). Phenyl vinyl ketone (PVK) was prepared fay the dehydrochlorlnatlon of 0 cbloro propiophenone (Eastman Kodak). Phenyl isopropenyl ketone (PPK) was prepared by the Mannich reaction using propiophenone, formaldehyde and dimethylamine HCl. 

Methyl Ethyl Ketone (Butanone) from 1- and 2-Butene... 

Despite the utilization of polyoxometallates as Bnansted acid catalysts in organic synthesis [13], the most important application is the palladium-catalyzed Wacker oxidation of ethylene to acetaldehyde in aqueous phase. Under standard conditions (PdCl2, CuCl2, 02, HC1), chlorine ions are corrosive and produce chlorinated by-products (mainly from CuCl2) these conditions are not suitable for the oxidation of higher olefins, such as 1-butene to methyl ethyl ketone. For this reason... 

In the manufacture of oxygenated solvents, the typical chemical reactions are hydration, dehydration, hydrogenation, dehydrogenation, dimerization and esterification. For example methyl ethyl ketone is manufactured from 1-butene in a two step reaction. First, 1-butene is hydrated to 2-butanol then a dehydrogenation step converts it to methyl ethyl ketone. The production of methyl isobutyl ketone requires several steps. First acetone is... 

The main uses of 1-butene, 1-hexene, and 1-octene are in the manufacture of linear low-density polyethylene (LLDPE) (see Section 6.1.1). Butene is also used in the manufacture of solvents such as methyl ethyl ketone or secondary butyl alcohol. Apart from LLDPE, 1-octene is used in the manufacture of isononyl alcohol (see Section 5.2). 

Due to the vast synthetic utility of annulation reactions, there are numerous analogous sequences that can be performed to reach the same class of products as the Wichterle reaction. The most notable of which is the Robinson annulation, which uses methyl vinyl ketone in place of 1,3-dichloro-2-butene. Later research has elaborated on the Wichterle reagent by constructing an extensive library of methyl vinyl ketone surrogates 9-14 that can be employed in a manner analogous to l,3-dichloro-2-butene. Despite the development of annulation reagents like 9-14, 1,3-dichloro-2-butene retains ample synthetic utility due to both its commercial availability and its ability to be trivially prepared from ethyl acetoacetate or methyl acetoacetate. ... 

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