3-fluoro-5-formylbenzonitrile

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

Procedure: (7-chloro-3-oxo-1,3-dihydroisobenzofuran-1-yl)triphenylphosphonium bromide (101) (2.88 g, 6.71 mmol) and 3-fluoro-5-formylbenzonitrile (1.0 g, 6.71 mmol) were dissolved DCM (60 mL), to this was added triethylamine (1.215 mL, 8.72 mmol) and the reaction was stirred overnight. The reaction mixture was evaporated to afford a brown solid. To this was added water (40 mL), EtOH (40 mL) and DMF (4 mL). Hydrazine hydrate (3.36 g, 67.06 mmol) was added and the reaction was heated at reflux overnight. The reaction was cooled and the precipitate was collected by filtration, washed with EtOH (25 mL) and air dried to afford the desired material as a yellow solid (1.260 g, 59.9% yield), which was used without further purification; 1H NMR (400.132 MHz, DMSO) δ 4.68 (2H, s), 7.49 (1H, d), 7.58 (1H, s), 7.68 (1H, d), 7.82 (1H, t), 7.99 (1H, dd), 8.34 (1H, dd), 12.82 (1H, s); m/z (LC-MS, ESI−), RT=2.21 (M−H 312). The reaction mixture was evaporated to afford a brown solid the reaction was heated at reflux overnight The reaction was cooled the precipitate was collected by filtration washed with EtOH (25 mL) and air dried

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

Procedure: 5-Cyano-3-fluorobenzaldehyde (4 g, 26.8 mmol) was dissolved in hydrazine hydrate and stirred at room temperature for 18 hours. The solution was poured onto ice and the resultant solid was separated by filtration and then dried under vacuum at 60° C. to afford the title compound (1.27 g) as a pink solid. Further material was isolated from the aqueous layer. MS (ES): C8H5N3 requires 143; found 144 (MH+). The solution was poured onto ice the resultant solid was separated by filtration dried under vacuum at 60° C.

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

Procedure: (7-chloro-3-oxo-1,3-dihydroisobenzofuran-1-yl)triphenylphosphonium bromide (101) (2.88 g, 6.71 mmol) and 3-fluoro-5-formylbenzonitrile (1.0 g, 6.71 mmol) were dissolved DCM (60 mL), to this was added triethylamine (1.215 mL, 8.72 mmol) and the reaction was stirred overnight. The reaction mixture was evaporated to afford a brown solid. To this was added water (40 mL), EtOH (40 mL) and DMF (4 mL). Hydrazine hydrate (3.36 g, 67.06 mmol) was added and the reaction was heated at reflux overnight. The reaction was cooled and the precipitate was collected by filtration, washed with EtOH (25 mL) and air dried to afford the desired material as a yellow solid (1.260 g, 59.9% yield), which was used without further purification; 1H NMR (400.132 MHz, DMSO) δ 4.68 (2H, s), 7.49 (1H, d), 7.58 (1H, s), 7.68 (1H, d), 7.82 (1H, t), 7.99 (1H, dd), 8.34 (1H, dd), 12.82 (1H, s); m/z (LC-MS, ESI−), RT=2.21 (M−H 312). The reaction mixture was evaporated to afford a brown solid the reaction was heated at reflux overnight The reaction was cooled the precipitate was collected by filtration washed with EtOH (25 mL) and air dried