Chloromethyl Methyl Ether → Methyl 3-methoxy-2,2-dimethylpropanoate

Participants

Reaction Conditions

Reaction Steps

To a solution of diisopropylamine (8.71 g, 86.1 mmol) in anhydrous THF (130 ml) was added under argon atmosphere a solution of n-butyl lithium in hexane (1.62N, 53.1 ml, 86.1 mmol) at -20° C. The reaction mixture was stirred for 30 min. and cooled to -78° C. To the reaction mixture were added a solution of methyl isobutyrate (8.00 g, 78.3 mmol) in 15 ml of anhydrous THF and HMPA (14.0 g, 78.3 mmol), and the mixture was stirred for one hour at -78° C. To this was added a solution of chloromethyl methyl ether (7.57 g, 94.0 mmol) in 15 ml of anhydrous THF, and the reaction mixture was stirred for 2 hrs. at -78° C. To an aqueous saturated solution of ammonium chloride (300 ml) were added the above solution and water (100 ml). The resulting mixture was extracted with ether (400 ml). The aqueous layer was reextracted with ether (200 ml×2). The combined ether layers were washed with water (300 ml) and with brine, and dried over anhydrous magnesium sulfate. Ether was distilled out at normal pressure and the residue was distilled (b.p. 98°-99° C./107 mmHg) to give methyl 2,2-dimethyl-4-oxapentanoate (8.38 g, 57.4 mmol, 73.3%) as an oily material. The product was assigned the structure by the following data.

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