A. t-Butyl azidoacetate. In a 300-ml. round-bottomed flask fitted with a reflux condenser are placed 30 g. (0.2 mole) of t-butyl chloroacetate (Note 1), 24 g. (0.37 mole) of sodium azide, and 90 ml. of 60% (v./v.) acetone-water. The heterogeneous mixture (two liquid phases and a solid phase) is heated under reflux on a steam bath for 18 hours, the acetone distilled, and 15 ml. of water added (Note 2). The mixture is transferred to a separatory funnel, the layers separated, and the lower aqueous layer extracted twice with 25-ml. portions of ether. The ethereal extracts are added to the original upper layer, and the solution is dried over anhydrous sodium sulfate. The ether is distilled, and the residual oil is fractionated under reduced pressure (Note 3), the fraction boiling from 33–41° (1 mm.) being collected; yield 29 g. (92%), n²⁰D 1.4356 (Note 4).

B. Glycine t-butyl ester. In the center neck of a 500-ml. suction filtration flask is placed a gas-inlet tube which is connected to a nitrogen cylinder, and on the side arm of the flask there is attached an exit tube leading to a suitable ventilation duct. The flask is placed on a magnetic stirrer, and a solution of 28.9 g. (0.18 mole) of t-butyl azidoacetate in 150 ml. of methanol and 0.7 g. of 5% palladium-on-charcoal catalyst is added to the flask. A stream of nitrogen is swept over the surface of the stirred suspension for 5 minutes, the nitrogen cylinder is replaced by a hydrogen cylinder, and hydrogen is passed over the magnetically stirred mixture for 10 hours. The hydrogen is displaced from the flask by a sweeping with nitrogen, the catalyst is removed by filtration and is washed with 5 ml. of methanol. The filtrate is transferred to a 500-ml. Erlenmeyer flask, 15 g. (0.18 mole) of phosphorous acid is added, and the mixture is warmed gently to dissolve the phosphorous acid. The solution is cooled to room temperature (Note 5), 150 ml. of ether is added slowly, and the solution is cooled at 0° for 12 hours. The precipitated glycine t-butyl ester phosphite is filtered, washed with ether, and dried in a vacuum oven at 70°, yield 29–32 g. (75–82%), m.p. 144–147° (dec.) (Note 6) and (Note 7).

To 50 ml. of a well-cooled 6N sodium hydroxide solution is added, with stirring, 32 g. (0.15 mole) of the phosphite salt. The stirring is continued until all the solid has dissolved. The solution is transferred to a 125-ml. separatory funnel, extracted with three 20-ml. portions of ether, and the combined extracts dried over anhydrous sodium sulfate. The drying agent is removed by filtration, the solvent removed under reduced pressure, and the glycine t-butyl ester distilled, b.p. 65–67° (20 mm.), n²⁰D 1.4237, yield 14 g. (72%, based on phosphite salt). The overall yield from t-butyl chloroacetate is 50–55%.