Aniline → 2-[(Diphenylmethyl)sulfanyl]aniline

Participants

Reaction Conditions

Reaction Steps

To a rapidly stirred solution of 2.3 g. (0.025 mole) of aniline and 10.0 g (0.050 mole) of benzylphenylsulfide in 300 ml. of dry acetonitrile and 100 ml. of methylene chloride under nitrogen at -40° C., was added dropwise 3.5 g. (0.032 mole, 28% excess) of tert-butylhypochlorite in 25 ml. of methylene chloride at -78° C. in diffuse light. The reaction mixture was stirred 4 hours at -40° C. then allowed to warm slowly to -20° C. over 3 hours. Sodium methoxide (7.0 g., 0.13 mole) in 50 ml. of dry methanol (at 25° ) was added quickly. The reaction mixture was stirred for 1 hour as it warmed to room temperature. The solution was concentrated in vacuo, 100 ml. of water was added, and extracted with 5 × 100 ml. of chloroform. The combined organic phases were washed with 50 ml of 5% aqueous sodium hydroxide, 100 ml. of saturated sodium chloride solution, dried over anhydrous magnesium sulfate, and filtered. Solvent was removed in vacuo giving a dark brown oil which was chromatographed on 300 g. of Fisher basic alumina (Act I) using etherpentane as eluant. Recovered was 5.2 g. (72% yield based on starting aniline) of 2-aminodiphenylthiophenoxymethane. Recrystallizaton from ethanol-water gave light yellow crystals, m.p. 64°-65.50°; ir (cm-1) (CCl4) 3480, 3380, 3090, 1620, 1580, 1490, 1450, 1310, 1270, 1160, 1080, 1070, 1025, 690; NMR (CCl4) τ: 2.4-3.7 (14H, m), 4.51 (1H, s), 6.0-6.4 (2H, br s).

Provenance & Evidence