Amines. 2-Phenylethyl Benzoate via the Nitrosoamide Decomposition

DEAMINATION OF AMINES. 2-PHENYLETHYL BENZOATE VIA THE NITROSOAMIDE DECOMPOSITION 

Cautiont Dinitrogen tetroxide is extremely toxic and should only he handled in an excellent hood. 

N-(2-Phenylethyl)benzamide. To a solution of 12.1 g. (0.10 mole) of 2-phenylethylamine and 7.9 g. (0.10 mole) of pyridine in a 250-ml. Erlenmeyer flask, immersed in an ice bath is added, slowly with stirring, 15.5 g. (0.11 mole) of benzoyl chloride. The resulting crystalline mixture is extracted with 

N-Nitroso-N-(2-phenylethyl)benzamide. A solution of 10.4 g. (0.046 mole) of the crude N-(2-phenylethyl)benzamide, 7.36 g. (0.09 mole) of anhydrous sodium acetate, and-50 ml. of glacial acetic acid is placed in a 250-ml. Erlenmeyer flask equipped with a drying tube, and the mixture is cooled to the crystallization point of the acetic acid (Note 1). A solution of dinitrogen tetroxide (Notes 2, 3) in glacial acetic acid (85 ml. of a solution approximately 1M in N2O4) is then added with stirring. The reaction mixture is allowed to warm to about 15° (15 minutes), and then it is poured into a mixture of ice and water. The yellow solid nitroso derivative is dissolved in 75 ml. of carbon tetrachloride, and this solution is washed with 5% sodium bicarbonate, water, and dried. The solution is used directly in the next step. 

If the nitroso derivative is desired, the yellow solid is separated by filtration, washed with water, 5% sodium bicarbonate solution, water, and dried under reduced pressure at room temperature. The solid is recrystallized from ether to give yellow needles of pure nitrosoamide yield 7.5 g. (64%), m.p. 57-58° (dec.). 

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