2- Ethyl-4-methylcyclohexanone

Conversion into 3-ethyl-3-methylcyclohexanone. Prepare a solution of ethyl-magnesium iodide in 120 ml of ether from 18.7 g (0.77 mol) of dry magnesium turnings and 120 g (0.77 mol) of ethyl iodide in a 500-ml, three-necked round-bottomed flask equipped with a sealed stirrer unit, a pressure-equalising funnel and a reflux condenser. When all the magnesium has dissolved, clamp the flask in a cooling bath of Cardice-acetone and replace the condenser with a low-temperature-reading thermometer. When the temperature has fallen to... 

Although the enamine (30) underwent addition reaction with ethyl azido-dicarboxylate, it failed to add another mole of jS-nitrostyrene. In a similar manner the morpholine enamine of 2-methylcyclohexanone also failed to react with this olefin, i.e., jS-nitrostyrene, which is undoubtedly due to the 1,3-diaxial interaction between the methyl group and the incoming electrophile in the transition state. 

This procedure appears to be general and has been successfully applied to the following examples ethyl acetoacetate from acetone (68 %) ethyl benzoylacetate from acetophenone (74%) ethyl a-propionylpropionate from diethyl ketone (81%) ethyl 2-methylcyclohexanone-6-carboxylate from 2-methylcyclohexanone (67%). 

Finally, with the aim of discovering novel chiral oxomolybdenum catalysts able to perform enantioselective alkene epoxidations, Kuhn et al. have reported the exploration of the catalytic behaviour of a series of dioxomolybdenum(VI) complexes with chiral cw-8-phenylthiomenthol ligands derived from ( + )-pulegone. Therefore, the epoxidation of c -p-methylstyrene using t-butyl-hydroperoxide as the oxidant and performed in the presence of ( + )-(2i ,5i )-2-[1-methyl-l-(phenylthio)ethyl]-5-methylcyclohexanone oxime as the ligand, did not produce, however, a significant optical induction in these conditions. 

The known examples of carbenoid insertion into an S—H bond have been supplemented by the Rh2(OAc)4-catalyzed synthesis of a-phenylthioketones from a-diazoketones and thiophenol 327). By this method, a number of primary and secondary acyclic a-diazoketones, ethyl diazoacetate and cyclic diazoketones such as 2-diazocyclopentanone, 2-diazo-6-methylcyclohexanone and 2-diazocyclohepta-none were converted at room temperature in good to high yield. 

Chloroethyl benzoate, 30,11 a-Chloroethyl ethyl ether, 36, 60 Chlorohydroquinone, 35, 27 -Chloromandelic acid, 35,14 Chloromethylation, 30, 68 2-Chloro-2-methylcyclohexanone, 37, 8... 

Silver fluoborate, reaction with ethyl bromide in ether, 46, 114 Silver nitrate, complexing with phenyl-acetylene, 46, 40 Silver oxide, 46, 83 Silver thiocyanate, 46, 71 Sodio-2-formyl-6-methylcyclohexanone, 48,41... 

Different stereoisomeric cyclohexanols resulted also from reduction of ethyl 4-/ r/-butyl-2-methylcyclohexanone-2-carboxylate with sodium borohydride (equatorial hydroxyl) or with aluminum isopropoxide (axial hydroxyl) [1088]. 

Chakrabarty et al. reported the syntheses of 9-carbethoxy-3-methylcarbazole (5) and 9-formyl-3-methylcarbazole (6) to confirm the assigned structures (17). The syntheses use 3-methylcarbazole (2) as a common intermediate, which was obtained under Fischer-Borsche conditions starting from phenylhydrazine (524) and 4-methylcyclohexanone (1006). Reaction of 3-methylcarbazole (2) with sodium hydride (NaH), followed by addition of ethyl chloroformate, afforded 9-carbethoxy-3-methylcarbazole (5). 9-Formyl-3-methylcarbazole (6) was obtained by reaction of 3-methylcarbazole (2) with formic acid (17) (Scheme 5.145). 

Explain why ethyl formate condenses with 2-methylcyclohexanone in the presence of base at the unsubstituted position ... 

Acetyl-n-valeric acid has been prepared by the oxidation of 1-methylcyclohexene with potassium permanganate 5 by the oxidation of 2-methylcyclohexanone with chromic oxide and sulfuric acid 6 by the reaction of methylzinc iodide on the ethyl ester of adipic acid chloride and saponification of the ethyl ester of 5-acetyl-w-valeric acid so obtained 7 by the saponification of the ethyl ester of diacetylvaleric acid 2 and through the hydrolysis of ethyl a-acetyl-6-cyanovalerate with boiling 20% hydrochloric acid.3... 

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