Triethylamine → N,N,N',N'-Tetraphenylurea

Participants

Reaction Steps

A solution of diphenylamine (3.05 g, 18 mmol) and triethylamine (6 mL, 43 mmol) in THF (62 mL) was added dropwise to a stirred solution of triphosgene (1.99 g, 6.7 mmol) in THF (37 mL) at room temperature. The reaction mixture was heated to reflux overnight. Then, a solution of diphenylamine (3.1 g, 18 mmol) and triethylamine (5.8 mL, 42 mmol) in THF (37 mL) was added. The reaction mixture was stirred overnight at reflux temperature. The reaction mixture was filtered and the filtrate was evaporated to dryness, yielding tetraphenylurea as a yellow solid. Yield: 6.0 g (91%). Oxalyl chloride (1.8 mL, 21 mmol) was added to a stirred solution of the urea (6.0 g, 16 mmol) in diethyl ether (65 mL). The reaction mixture was evaporated to dryness after stirring for 2 days at reflux. A solution of ammonia in methanol (5 mL, 35 mmol, 7 M) was added. The reaction mixture was heated to reflux overnight and evaporated to dryness. The product was neutralized and purified from ammonium chloride by several treatments with aqueous sodium hydroxide solutions. The organic layer was extracted and dried over sodium sulfate. Crystallization from diethyl ether at low temperature yielded the desired guanidine as a white solid. Yield: 2.0 g (33%). 13C NMR (CDCl3, 75 MHz): δ 121.4, 126.7, 128.6, 140.3, 164.5 ppm.

Provenance & Evidence