4-methyl-3-hexanone, from oxidation

Methylsuccinic acid has been prepared by the pyrolysis of tartaric acid from 1,2-dibromopropane or allyl halides by the action of potassium cyanide followed by hydrolysis by reduction of itaconic, citraconic, and mesaconic acids by hydrolysis of ketovalerolactonecarboxylic acid by decarboxylation of 1,1,2-propane tricarboxylic acid by oxidation of /3-methylcyclo-hexanone by fusion of gamboge with alkali by hydrog. nation and condensation of sodium lactate over nickel oxide from acetoacetic ester by successive alkylation with a methyl halide and a monohaloacetic ester by hydrolysis of oi-methyl-o -oxalosuccinic ester or a-methyl-a -acetosuccinic ester by action of hot, concentrated potassium hydroxide upon methyl-succinaldehyde dioxime from the ammonium salt of a-methyl-butyric acid by oxidation with. hydrogen peroxide from /9-methyllevulinic acid by oxidation with dilute nitric acid or hypobromite from /J-methyladipic acid and from the decomposition products of glyceric acid and pyruvic acid. The method described above is a modification of that of Higginbotham and Lapworth. ... 

In reactions carried out for 24 h at room temperature, a 95% yield of cyclo-hexanol from cyclohexanone was obtained. Other ketones and aldehydes were also hydrogenated under identical conditions, but with slower rates (38% conversion for hydrogenation of 2-hexanone, 25% conversion of acetophenone, 45% for 3-methyl-2-butanone). Insertion of the C=0 bond of the ketone or aldehyde into the Cr-H bond was proposed as the first step, producing a chromium alk-oxide complex that reacts with acid to generate the alcohol product. The anionic chromium hydride [(COJsCrH]- is regenerated from the formate complex by... 

Wittig reactions of cyclohexanone derivatives in their inclusion compounds with the chiral host 5 gave optically active reaction products. For example, when a mixture of finely powdered 1 1 inclusion compound of 5b with 4-methyl-(15a) or 4-ethylcyclo-hexanone (15b) and phosphorane (16) was kept at 70 °C, the Wittig reaction in the solid state was completed within 4 h. To the reaction mixture was added diethyl ether-petroleum ether (1 1), and then the precipitated triphenylphos-phine oxide was removed by filtration. The crude product left after evaporation of solvent from the filtrate was distilled in vacuo to give (-)-4-methyl- (17a) of 42% ee (73 % yield) or (-)-4-ethyl-l-(carboethoxymethylene)cyclohexane (17b) of 45 % ee (57 % yield), respectively [9], Similar reaction of the 1 1 inclusion compound of 5c and c /. v - 3,5 - dime th y I c y c I o h e x a n o n e (18) with 16 gave 19 of 57 % ee in 58 % yield [9],... 

In an aptly titled paper Herz et describe unexpected rearrangements of photolevopimaric acid derivatives. Among a wealth of chemical reactions discussed it appears that the exo-bicyclo[2,2,0]hexanol (575), derived from methyl levopimarate by hydroboration-oxidation, is rearranged during Jones oxidation to the bicyclo[2,l,l]-hexanone (576), contrary to a previous report. A mechanism is proposed. 

Hydrolysis of the labeled compound with 2 N sulfuric acid furnished 3-amino-4-methyl-2-hexanone which, on treatment with iodine in the presence of sodium hydroxide, furnished isoleucine and iodoform. The iodoform was oxidized to carbon dioxide, while treatment of isoleucine with ninhydrin furnished 2-methylbutanal, isolated as its 2,4-dinitrophenylhydrazone. Kuhn-Roth oxidation of the aldehyde gave acetic acid which was degraded by the Schmidt procedure to carbon dioxide and methylamine. The 2-methylbutanal was also degraded stepwise by the method of Strassman. Determination of the radioactivity of the various degradation products showed that 94% of the activity was equally shared between the lactam C(2) and side-chain C(10) carbonyl atoms. The remaining activity was shared between C(4) of the lactam ring and the a> carbon atom of the ec-butyl side chain. The results are consistent with derivation of tenuazonic acid from isoleucine and two molecules of acetic acid. However, the direct incorporation of isoleucine into tenuazonic acid was not investigated. 

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