3-[2-(2,5-difluorophenyl)hydrazinyl]propanenitrile

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 3-(2-(2,5-difluorophenyl)hydrazinyl)propanenitrile (790 mg) in 15 mL of 2N sulfuric acid was added 2.0 g of iron(III) sulfate hydrate. The reaction mixture was stirred at ambient temperature for 30 min as the iron sulfate slowly dissolved and a yellow oil precipitated. The reaction mixture was extracted with ether, and the extracts were washed with water, brine, dried over sodium sulfate, filtered through a plug of silica gel and concentrated to give 710 mg (91%) of (E)-3-((2,5-difluorophenyl)diazenyl)propanenitrile. LCMS (ESI) m+H=196.2. 1H NMR (400 MHz, CDCl3) δ 7.34-7.08 (m, 3H), 4.54-4.31 (m, 2H), 2.99 (t, 2H). slowly dissolved a yellow oil precipitated The reaction mixture was extracted with ether the extracts were washed with water, brine dried over sodium sulfate filtered through a plug of silica gel concentrated

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of acrylonitrile (10 mL), ethanol (20 mL) and 2,5-difluorophenylhydrazine (790 mg) was heated to reflux for 2 days. The reaction was concentrated under vacuum and the product purified by flash chromatography on silica gel with methylene chloride to give 790 mg (73%) 3-(2-(2,5-difluorophenyl)hydrazinyl)propanenitrile. LCMS (ESI) m+H=198.2; 1H NMR (400 MHz, CDCl3) δ 6.99 (ddd, 1H), 6.89 (ddd, 1H), 6.38 (tt, 1H), 5.45 (s, 1H), 3.91 (s, 1H), 3.19 (td, 2H), 2.61 (t, 2H). to reflux for 2 days The reaction was concentrated under vacuum the product purified by flash chromatography on silica gel with methylene chloride