Ketones methylation with

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 Amyl Ketone. Methyl amyl ketone [110-43-0] (MAK) (2-heptanone) is a colorless Hquid with a faint fmity (banana) odor. It is found in oil of cloves and cinnamon-bark oil, and is manufactured by the condensation of acetone and butyraldehyde (158). Other preparations are known (159-162). 

Methyl Isoamyl Ketone. Methyl isoamyl ketone [110-12-3] (5-methyl-2-hexanone) is a colorless Hquid with a mild odor. It is produced by the condensation of acetone and isobutyraldehyde (164) in three steps which proceed via the keto-alcohol dehydration to 5-methyl-3-hexen-2-one, and hydrogenation to 5-methyl-2-hexanone. 

Methyl Vinyl Ketone. Methyl vinyl ketone [78-94-4] (3-buten-2-one) is a colorless Hquid with a pungent odor. It is stable only below 0°C, and readily polymerizes on standing at room temperature. It can be inhibited for storage and transportation by a mixture of acetic or formic acid and hydroquinone or catechol (266). This ketone is completely soluble in water, and forms a binary azeotrope with water (85 MVK 15 H2O vol %) at 75.8°C. 

Two solvent processes for preparation of Ca(OCl)2 have been described. In one, a CCl solution of /-C H OCl is allowed to react with a thin lime slurry and the aqueous phase, a solution of Ca(OCl)2, is evaporated to a product with a purity of >95% (217). In the other, a solution of HOCl in methyl ethyl ketone reacts with either CaO or Ca(OH)2 (133). FoUowing filtration, the residual solvent in the product is removed under vacuum. 

Typical of these materials are the poly(vinyl thioethers), the poly(vinyl isocyanates), the poly(vinyl ureas) and the poly(alkyl vinyl ketones). Methyl isopropenyl ketone and certain vinylpyridine derivatives have been copolymerised with butadiene to give special purpose rubbers. 

The styrene double bond in 9(ll)-dehydroestradiol 3-methyI ether (1) or its 8-dehydro counterpart is reduced by potassium or lithium in ammonia without affecting the aromatic ring estradiol 3-methyl ether (2) is formed from both compounds. Reduction of the corresponding 17-ketones occurs with partial or complete reduction of the carbonyl group. Lithium... 

In the androstane and pregnane series the 7-methyl-A -3-ketones (36) are produced from 3j -acetoxy-A -7-ketones (34) with methyllithium, and subsequent Oppenauer oxidation of (35). ° ... 

Ethynylation of the totally synthetic racemic 18-methyl-17-ketone (63) with acetylene and potassium t-butoxide in t-butanol-toluene or with alkali metal acetylide in liquid ammonia gives a low yield of rac-18-methyl-17a-ethynyl-3-methoxyestra-l,3,5(10)-trien-17/ -ol (64). 

In a typical Knof procedure, 3jS-hydroxyandrost-5-en-17-one acetate is epoxidized with perbenzoic acid (or m-chloroperbenzoic acid ) to a mixture of 5a,6a- and 5)5,6)5-epoxides (75) in 99 % yield. Subsequent oxidation with aqueous chromium trioxide in methyl ethyl ketone affords the 5a-hydroxy-6-ketone (76) in 89% yield. Baeyer-Villiger oxidation of the hydroxy ketone (76) with perbenzoic acid (or w-chloroperbenzoic acid ) gives keto acid (77) in 96% yield as a complex with benzoic acid. The benzoic acid can be removed by sublimation or, more conveniently, by treating the complex with benzoyl chloride and pyridine to give the easily isolated )5-lactone (70) in 40% yield. As described in section III-A, pyrolysis of j5-lactone (70) affords A -B-norsteroid (71). Knof used this reaction sequence to prepare 3)5-hydroxy-B-norandrost-5-en-17-one acetate, B-noran-... 

Similar adducts are formed when the dienamine is allowed to react with methyl vinyl ketone and with methyl acrylate. 

Bohlmann (207) reported the reaction of /I -dehydroquinolizidine with methyl vinyl ketone and with propargyl aldehyde forming a partially saturated derivative of julolidine 135 and julolidine (136), respectively. Compound 135 can be prepared also by mercuric acetate dehydrogenation of ketone 137, which is formed by condensation of 1-bromoethylquinolizi-dine with ethyl acetoacetate (Scheme 11). 

The ability of 1,2 (or l,6)-dihydropyridines to undergo a Diels-Alder reaction with dienophiles such as methyl vinyl ketone, methyl acrylate, and acrylonitrile has been utilized in the synthesis of polyfunctional isoquinuclidine as a key intermediate in the synthesis of aspidosperma- and iboga-type alkaloids (66JA3099). 

The deprotonation of 4,5-dimethylthiazole and addition of the resulting anion to aldehydes was demonstrated as early as 1948 (48HCA652) and 2-lithiothiazoles were later shown to react with aldehydes, ketones, methyl iodide, and epoxides... 

Paulsen and Huck also used gas-phase chlorination of ammonia. The mixture, diluted with nitrogen, was led into excess liquid ketone. Diaziridines were obtained from methyl ethyl ketone, diethyl ketone, methyl propyl ketone, and methyl isopropyl ketone. The yields of the crude diaziridines, calculated on the chlorine, were over 90% (Table IV). 

The next step was to convert cyclohexanone-4-carboxylic acid into l-methyl-cyclohexanol-4-carboxylic acid, and this is readily accomplished by heating the ester of the ketonic acid with magnesium methyliodide in the usual manner—... 

As a symmetrical ketone, acetone is a reactive compound with many synthetic uses. Among the important chemicals based on acetone are methylisobutyl ketone, methyl methacrylate, ketene, and diacetone alcohol. 

Methyl phenyl sulfide, see Thioanisole Methyl phenyl sulfoxide, 46, 78 from methylsulfinyl chloride and benzene with anhydrous alumi num chloride, 46, 80 Methyl vinyl ketone, reaction with 1-morpholino 1 cyclohexene, 45,... 

However, addition of (+ )-(7 )-l-methyl-4-(mcthylsulfinyl)benzene, to aldehydes and ketones proceeds with low stereoselectivity. An improvement of the 3-syn diaslereoselectivity was found with the zinc reagent obtained by transmetalation of the lithiated sulfoxide with anhydrous zinc chloride38. An improvement of the stereoselectivity was also attained by exchange of the 4-methylphenyl substituent for a 2-methoxyphenyl or 2-pyridinyl substituent. Thus, the introduction of an additional complexing site into the aromatic part of the sulfoxide reagent enhances the stereoselectivity35. 

Furyl methyl ketone was also tried with a series of olefins inhibition was operative in all systems and only traces of a copolymer with acenaphthylene were isolated at the end of a run which lasted several days. These observations are compatible with the higher basicity of this ketone compared with that of the corresponding aldehyde. 

Methyl vinyl ketone, condensation with 2-methyl-l,3-cyclohexanedione, 41, 38... 

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