- Preparation of Cyclohexyl methyl ketone
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(CAS no.: ), which is also known as Ketone, cyclohexyl methyl, could be produced through the following synthetic routes.
Caution! Since hydrogen is liberated in the first step of this reaction, it should be conducted in a hood. A dry, 500-ml., three-necked flask is fitted with a reflux condenser, a pressure-equalizing dropping funnel, a mechanical stirrer, and an inlet tube to maintain a static nitrogen atmosphere in the reaction vessel throughout the reaction. In the flask are placed 1.39 g. (0.174 mole) of powdered lithium hydride and 100 ml. of anhydrous 1,2-dimethoxyethane. While this suspension is stirred vigorously, a solution of 19.25 g. (0.150 mole) of cyclohexanecarboxylic acid in 100 ml. of anhydrous 1,2-dimethoxyethane is added dropwise over a 10-minute period. The resulting mixture is heated to reflux with stirring for 2.5 hours, at which time hydrogen evolution and the formation of lithium cyclohexanecarboxylate are complete. After the resulting suspension has been cooled to approximately 10° with an ice bath, it is stirred vigorously while 123 ml. of an ethereal solution containing 0.170 mole of methyllithium is added dropwise over a 30-minute period. After the addition is complete, the ice bath is removed and the resulting suspension is stirred at room temperature for 2 hours. The dropping funnel is removed from the reaction flask and replaced by a rubber septum fitted with a 4-mm. O.D. glass tube of suitable dimensions to permit the reaction mixture to be siphoned from the reaction flask when a slight positive nitrogen pressure is present in the flask.
The fine suspension in the reaction flask is agitated and siphoned into a vigorously stirred mixture of 27 ml. (0.32 mole) of concentrated hydrochloric acid and 400 ml. of water. The reaction flask is rinsed with an additional 100 ml. of ether which is also added to the aqueous solution. After the resulting mixture has been saturated with sodium chloride, the organic phase is separated and the alkaline aqueous phase is extracted with three 150-ml. portions of ether. When the combined organic solutions have been dried over magnesium sulfate, the bulk of the ether is distilled from the mixture through a 40-cm. Vigreux column and then the residual ether and the 1,2-dimethoxyethane are distilled from the mixture through a 10-cm. Vigreux column. Distillation of the residual pale yellow liquid separates 17.1–17.7 g. (91–94%) of the methyl ketone as a colorless liquid, b.p. 57–60° (8 mm.), n26D 1.4488–1.4489.
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