4- Methyl-3-hexanone

Menthone has been prepared synthetically by Kotz and Hesse from methyl hexanone. This body was condensed with ethyl oxalate by adding... 

Use the apparatus detailed in Section 111,20. Dissolve 100 g. (123 ml.) of methyl n-butyl ketone (2-hexanone) (Section 111,152) in 750 ml. of ether and add 150 ml. of water. Introduce 69 g. of clean sodium in the form of wire (or small pieces) as rapidly as possible the reaction must be kept under control and, if necessary, the flask must be cooled in ice or in running water. When all the sodium has reacted, separate the ethereal layer, wash it with 25 ml. of dilute hydrochloric acid (1 1), then with water, dry with anhydrous potassium carbonate or with anhydrous calcium sulphate, and distil through a fractionating column. Collect the fraction of b.p. 136-138°. The yield of methyl n-butyl carbinol (2-hexanol) is 97 g. 

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. 

Hexanone Methyl n-butyl ketone 127 CsHijO p-Xylene 1,4-Dimethylbenzene 71 QHio... 

Syn 3-(EthyltHloniethyl)-4-hydroxy-6-pt)enyl-2-hexanone (4) and anti (5) To ethanethiol (10 0 mg 0 17 mmol) in THF (2 mL) was added 1 54 M n butyltittnum m hexane (0 11 mL) at 0 C under Ar Stannous triflate (69 0 mg 017 nvnol) was added and alter 20 mm the mocture was cooled to 4S°C Methyl vinyl Ketone 1 (118 mg 1 98 mmol) m THF (1 5 mL) was added followed by 3 phenyiptopanal 3 350 mg 2 61 mmol) m THF (1 S mL) Alter 12 h aq cilnc acid was added and the organic material extracted with OHjClj The resxlue after evaporation was dissolved in MeOH and treated with citric acxt After 30 min stimng, the mixture was quenched with pH 7 phosphate buffer extracted with CH2CI2, the solvent evaporated and the residue chromatographed to afford 336 mg ot 4 (75%), syn anti (90 10)... 

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. ... 

Quantum yield data for several processes that occur on photolysis of 5-4-methyl-1-phenyl-l-hexanone have been determined. The results are tabulated below for benzene as solvent. 

Hexanolactam, see Caprolactam 2-Hexanone, see Methyl n-butyl ketone 1 -Hexene... 

Methyl butyl ketone, see 2-Hexanone Methyl cellosolve, see 2-Methoxyethanol Methyl cellosolve acetate, see Ethylene glycol monomethyl ether acetate... 

Chemical Designations - Synonyms n-Butyl methyl ketone 2-Hexanone Chemical Formula CH3(CHj)3COCH3... 

That the methyl group in the pyrrolidine enamine of 2-methylcyclo-hexanone (7) is in fact axial was demonstrated by Johnson and Whitehead (8). They found that careful hydrolysis of the pyrrolidine enamine of the conformationally more stable system, i.e., 2-methyI-4-t-butylcyclohexanone (13), led to a 1 4 mixture of cis and trans isomers of the ketone (14 and 15), showing that the methyl group in the enamine is largely in the axial orientation. 

On the other hand there have been isolated salts of either the acyclic amino ketone form or the cyclic enamine form, namely 6-methylamino-l-a-naphthyl-l-hexanone (95, = 5) and 12-methylamino-l-a-naphthyl-l-dodecanone (95, n=ll), or l-methyl-2-a-naphthyl-l-aza-2-cycloheptene... 

The synthesis of the 1-methyl derivative of sempervirine was achieved by Woodward and McLamore who condensed 1-lithio-methyl-9-methyl-jS-carboline (386) with 2-isopropoxymethylenecyclo-hexanone (387) treatment of the reaction product with hydrochloric acid gave im -W-methylsempervirinium chloride (cf. 388). 

Methyl-l-hexanone-3, C-HjjO, is found naturally in pennyroyal oil, and is obtained by the decomposition of pulegone. It is an aromatic liquid having the following characters —... 

Wallach has synthesised i-menthone by condensing 1, 4-methyl-cyclo-hexanone with bromo-isobutyric ester from the condensation product he prepared i-menthene, which was converted into i-menthenone, by means of its nitrosochloride, whence i-menthone resulted by reduction. 

Figure 19.19 Mass spectr um of 5-methyl-2-hexanone. The peak at m/z = 58 is due to McLafferty rearrangement. The abundant peak at mlz = 43 is due to ct cleavage at the more highly substituted side of the carbonyl group. Note that the peak due to the molecular ion is very small.

Methylene 2 hexanone, 47, 87 5 Methyl 5 hexen 2-one, 47, 87 Methyl hvdrazine, 46, 85 Methyl isocyanide, 46, 7S Methy lmagnesium bromide, reaction with bis(10,9 borazarophenan-thryl) ether, 46, 67 reaction w ith thiophosphoryl chloride, 45,102... 

THF (10 ml) was added to the above solution of TMSLi in HMPA, and the mixture immediately cooled to —78°C. A solution of cyclohex-2-enone 1.5mmol) in THF (1ml) was then added dropwise. After stirring for an additional 5 min, methyl iodide (0.5 ml, excess) was added, and the mixture allowed to warm slowly to 0°C. It was then poured into pentane (50 ml) and washed thoroughly with water (2 x 25 ml). After drying and concentration, the residual oil was distilled to give trans-3-trimethylsilyl-2-methylcyclo-hexanone (97%), b.p. 80°C/1 mmHg (Kugelrohr). 

The product of Part B of this procedure, methyl 7-oxoheptanoate, has previously been synthesized from cyclohep-tanone in two steps with a 42% overall yield." 7-Oxooctanoic acid, the methyl ester of which is the product of Part C, has been prepared by base-induced ring cleavage of 2-acetylcyclo-hexanone."... 

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