Dichloromethane → HCID 59349482, compound

Participants

Reaction Steps

A single necked 50 ml flask fitted with a Teflon stirrer, Claisen head fitted with a rubber septa and reflux condenser was charged with iron powder (Aldrich, 6.2 mmoles, 3 equivalents, 0.358 g) and an aqueous solution of ammonium chloride (10.70 mmoles, 5 equivalents, 0.573 g). The slurry was rapidly stirred and a solution of 2-nitro-4-(pyridin-4-ylmethoxy)aniline (2.14 mmoles, 0.525 g) in methanol (10 ml, 5 ml./mmole of nitro compound) was prepared with gentle heating to ensure complete dissolution. The methanolic solution of methyl 2-nitro-4-(pyridin-4-ylmethoxy)aniline was added over a period of 10 minutes using a syringe and needle. Upon completion of addition the reaction mixture was brought to a gentle reflux and the progress of the reaction was monitored by TLC (silica, 100% ethyl acetate or dichloromethane, visualizing by UV). After 1.5 hours, additional iron powder (Aldrich, 6.2 mmoles, 3 equivalents, 0.358 g), ammonium chloride (10.70 mmoles, 5 equivalents, 0.573 g) and methanol (10 ml) was added. The reaction was found to be complete after 2.5 hours. A sintered filtered funnel (60 ml, medium grade sintered) was packed with Celite (20 mm thick) and connected to a Buchner flask. The hot reaction mixture was filtered through the pad of Celite, the flask rinsed with hot methanol (2×25 ml), filtered and the filtered pad washed with more hot methanol (2×40 ml). The combined filtrate was evaporated to dryness. The recovered material was dissolved in 50 ml cold water and 100 ml dichloromethane and allowed to separate. The dichloromethane layer was dried over sodium sulfate, filtered and evaporated under reduced pressure to give 0.497 of 4-(pyridin-4-ylmethoxy)benzene-1,2-diamine which was used in the next step without any further purification. 1H-NMR (400 MHz, DMSO-d6) 10.50 (br s, 4H), 7.68 (d, 2H), 7.42 (m, 2H), 6.60 (d, 1H), 6.41 (s, 1H), 6.22 (d, 1H), 5.12 (s, 2H). (MS (EI): 216 (MH+).

Provenance & Evidence