2,4,5-Trichloroaniline → 2,2',4,5,5'-Pentachloro-4'-methoxy-1,1'-biphenyl

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Reaction Steps

To a suspension of 2,4,5-trichloroaniline (1.96 g, 10 mmol) in 30 mL 35% H2SO4 in an ice/salt bath (below 0° C.) was added a solution of sodium nitrite (0.828 mg, 12 mmol) in 50 ml cold distilled water. The yellow mixture was allowed to stir below 0° C. for 45 minutes at which time it was added to a vigorously stirred solution of 2,5-dichloroanisole (1.76 g, 10 mmol) in 100 mL CCl4 below 0° C. Saturated sodium acetate solution was added until a pH≧7 was obtained. The resulting mixture was allowed to warm to room temperature, then stirred 18 h. The reaction was extracted with several portions of CH2Cl2 and the combined organic layers were dried with anhydrous Na2SO4, filtered, then concentrated to a heavy oil. The oil was distilled (150-200° C., 0.2 mm Hg) through a Kugelrhor apparatus to yield 0.8 g of a dark yellow oil. The distillate was further purified via flash chromatography (silica gel, hexane eluent). Fraction 1 (40 mg; Rf=0.38; GC retention time=16.32 minutes) was identified as 2,2′,4′,5,5′-pentachloro-6-methoxybiphenyl. Fraction 2 (262 mg, 7.4% yield; Rf=0.33) was found to contain 2,5,2′,4′,5′-pentachloro-3-methoxy and 2,5,2′,4′,5′-pentachloro-4-methoxybiphenyl in a 17:83 ratio as determined by GC (RT=17.58, 17.75 minutes respectively) and NMR analyses.

Provenance & Evidence