2G81sealed stirrer, and dropping funnel, and covered with ether. Ethyl bromide (7.4 g., 0.068 mole) in 100 ml. ether was added dropwise and the reaction mixture boiled for 1 hr. 3-Methoxy-3-methyl-1-butyne (4.9 g., 0.05 mole), disaolved in 70 ml. of ether, was then added dropwise with stirring. The mixture was boiled for 4 hr., cooled, and 9.4 g. (0.05 mole) of benzophenone dissolved in 100 ml. of ether was added dropwise with stirring in 30 min. The reaction mixture was stirred overnight at room temperature, boiled for 4 hr., cooled, and hydrolyzed by elow addition of 100 ml. of ice water. Approximately 10 g. of ammonium chloride was added in portions with stirring to the suspension until two clear layers separated. The ethereal layer was separated, mashed with two 200-ml. portions of cold water and dried over :ttihydrous potassium carbonate.The ettier was removed by distillation leaving an oily residue which solidified on standing. The solid was dissolved in boiling petroleum ether (b.p. 60-90') and on cooling, white needles precipitated. The precipitate was collected by filtration and dried; 8.5 g. (61% yield), m.p. 87-89.5". Two recrystallizations from petroleum ether gave white needles, m.p. 85-86.5". Anal. Calcd. for CI~HZ002: C, 81.40; H, 7.19. Found: C, 81.51 ; H, 7.07. The infrared spectrum had bands a t 2.8, 4.5, and 8.5 p for -OH, -C=C-, and tertiary C--0 respectively. 4-Methozy-4-methyl-$?-pentynoic acid. Ethylmagnesium bromide was prepared from 37 g. (0.34 mole) of ethyl hromide and 8 g. (0.33 g.-atom) of magnesium turnings in ether in a 1-I., three-neck flask fitted with mercury sealed stirrer,dropping funnel, and reflux condenser. Twenty-four grams (0.25 mole) of 3-methoxy-3-methyl-1-butyne in 100 ml. of ether was added dropwise with stirring over a period of 2 hr. The mixture was boiled for 3 hr. and then cooled to room temperature. The dropping funnel was replaced by a gas inlet tube and carbon dioxide, dried with sulfuric acid, was admitted for 16 hr. with stirring. The mixture was hydrolyzed with 200 ml. of ice water and ca. 300 ml. of 10% hydrochloric acid. The mixture was stirred until two clear layers were formed. The lower layer was withdrawn and extracted with two 100-ml. portions of ether. The ether extracts were combined and washed with three 100-ml. portions of water and dried over anhydrous sodium sulfate. After evaporation of the ether, the dark residue was distilled and gave 14.6 g. (41% yield) of a viscous liquid, b.p. 99-103"/0.5 mm., ny 1.4580. This liquid, which turned yellow shortly after distillation, was soluble in water, 10% sodium hydroxide solution, and evolved carbon dioxide when added to a 10% sodium bicarbonate solution.The pphenylphaacyl ester was prepared by adding 10% sodium hydroxide dropwise to a mixture of 5 ml. of water and 1 g. of the acid contained in 50 ml. round-bottom flask fitted with reflux condenfier until the solution was neutral. Two drops of the acid were then added to make the solution slightly acidic. Ethanol (10 ml.) and 1 g. of p-phenylphenacyl brom...
