S-Pyrrolidinemethanol (XI). Freshly cut sodium metal(1.15 g., 0.05 g.-atom) was covered with 5 ml. of dry toluene and the mixture heated to slow reflux with efficient stirring, while a combined solution of ethyl 3-pyrrolidinecarboxylate (1.4 g., 0.01 mole), 4-methylpentanol-2 (2.62 g., 0.025 mole), and 15 ml. of dry toluene was added dropwise over a 1-hr. period. After being stirred and refluxed for 2 hr., the reaction mixture was cooled to 50-60°and carefully decomposed with 10 ml. of water. The organic layer was separated. The aqueous layer was saturated with solid potassium hydroxide and extracted several times with toluene. The toluene extracts were combined and dried over anhydrous magnesium sulfate. The oily residue which was obtained after filtering and concentrating the toluene solution was distilled under reduced pressure to collect 0.30 g. (30%) 3-pvrrolidinemethanol as a colorless distillate, b.p. 122°a t 15 mm., n1 2 3D" 1.4851. l-Methyl-3-pyrrolidinemethanol. A mixture of 3-pyrrolidinemethanol (300 mg., 3 mmoles), formic acid (380 mg., 8 mmoles), and formaldehyde (37%, 270 mg., 3 mmoles) was refluxed for 6.5 hr. Concentrated hydrochloric acid (600 mg., 7 mmoles) was added and the refluxing continued for 30 min. The residue, obtained by concentrating the mixture in a partial vacuum, was cooled in an ice bath, made strongly basic with 0.5 ml. of 40% sodium hydroxide, and extracted thoroughly with ether. The ethereal extract was dried over anhydrous magnesium sulfate, filtered, and concentrated to an oily residue. l-Methyl-3-pyrrolidinemethanol (120 mg., 35%) was obtained as a colorless oil by fractional distillation, b.p. 93-95°at 16 mm., " 1.4682.1-MethyUS-pyrrolidinemethanot methobromide. A solution of l-methyl-3-pyrrolidinemethanol (120 mg., 1 mmole) in 0.5 ml. of acetonitrile was cooled in an ice bath and saturated with methyl bromide. l-Methyl-3-pyrrolidinemethanol methobromide separated as white crystals which were filtered and washed with a 0.5-1 ml. amount of isopropyl alcohol. After drying at 60°for 1 hr., l-methyl-3-pyrrolidinemethanol methobromide (110 mg., 52%) melted at 250-253°. A mixed melting point determination with an authentic sample showed no depression.18Acknowledgment. The authors wish to thank Dr. J. R. Corrigan of these laboratories for his technical assistance and many useful suggestions.They are also indebted to Mr. Richard E. Miner of Metal Hydrides Incorporated, Beverly, Mass., for a sample of sodium aluminum hydride.Evansville 21, Ind.(18) See Table II, footnote a.
