2-fluoro-3-iodobenzaldehyde

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of diisopropylamine (10.42 mL, 74.36) in THF (135 mL) under N2 in an ice bath at 0-5° C. was added dropwise over 10 min n-BuLi (42.25 mL, 67.6 mmol) and stirred at this temperature for 10 min. Cooled the reaction mixture to −78° C. in a dry ice/acetone bath and dropwise added 1-fluoro-2-iodobenzene (7.88 mL, 67.6 mmol) over 5 min. Stirred at this temperature for 1 h, dropwise added DMF (6.26 mL, 74.36 mL) over 5 min, and stirred for 10 min. Added Acetic Acid (13.5 mL) followed by H2O and extracted with Et2O (2×). The combined organic solution was washed (0.1 N HCl then brine), dried (MgSO4), filtered and concentrated. The crude benzaldehyde (16.9 g) was taken onto the next step without purification. 1H NMR was consistent with structure. Stirred at this temperature for 1 h stirred for 10 min extracted with Et2O (2×) The combined organic solution was washed (0.1 N HCl brine), dried (MgSO4) filtered concentrated The crude benzaldehyde (16.9 g) was taken onto the next step without purification

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of diisopropylamine (10.42 mL, 74.36) in THF (135 mL) under N2 in an ice bath at 0-5° C. was added dropwise over 10 min n-BuLi (42.25 mL, 67.6 mmol) and stirred at this temperature for 10 min. Cooled the reaction mixture to −78° C. in a dry ice/acetone bath and dropwise added 1-fluoro-2-iodobenzene (7.88 mL, 67.6 mmol) over 5 min. Stirred at this temperature for 1 h, dropwise added DMF (6.26 mL, 74.36 mL) over 5 min, and stirred for 10 min. Added Acetic Acid (13.5 mL) followed by H2O and extracted with Et2O (2×). The combined organic solution was washed (0.1 N HCl then brine), dried (MgSO4), filtered and concentrated. The crude benzaldehyde (16.9 g) was taken onto the next step without purification. 1H NMR was consistent with structure. Stirred at this temperature for 1 h stirred for 10 min extracted with Et2O (2×) The combined organic solution was washed (0.1 N HCl brine), dried (MgSO4) filtered concentrated The crude benzaldehyde (16.9 g) was taken onto the next step without purification

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: A 50% aqueous solution of hydroxylamine hydrochloride (9 mL, 64.8 mmol) was added to a stirred suspension of 2-fluoro-3-iodobenzaldehyde (preparation 22d, 2.10 g, 8.4 mmol) in ethanol (10 mL) and the mixture was warmed slightly until a solution was formed. After stirring for 3 days at room temperature, the mixture was concentrated in vacuo and water was added to the residue. The mixture was extracted with ethyl acetate and the organic layer was washed with brine, dried (MgSO4) and evaporated to give the title compound (2.15 g, 97%) as a solid. the mixture was warmed slightly until a solution was formed the mixture was concentrated in vacuo and water was added to the residue The mixture was extracted with ethyl acetate the organic layer was washed with brine dried (MgSO4) evaporated

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Manganese (IV) oxide (15.40 g, 177 mmol) was added portionwise to a stirred solution of (2-fluoro-3-iodophenyl)methanol (preparation 22c, 4.03 g, 16 mmol) in dichloromethane (140 mL) and the mixture was stirred at 50° C. After 3 hours, the mixture was filtered through Celite® and the solvent was evaporated to give the title compound (2.10 g, 53%) as a white solid. the mixture was filtered through Celite® the solvent was evaporated

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of diisopropylamine (10.42 mL, 74.36) in THF (135 mL) under N2 in an ice bath at 0-5° C. was added dropwise over 10 min n-BuLi (42.25 mL, 67.6 mmol) and stirred at this temperature for 10 min. Cooled the reaction mixture to −78° C. in a dry ice/acetone bath and dropwise added 1-fluoro-2-iodobenzene (7.88 mL, 67.6 mmol) over 5 min. Stirred at this temperature for 1 h, dropwise added DMF (6.26 mL, 74.36 mL) over 5 min, and stirred for 10 min. Added Acetic Acid (13.5 mL) followed by H2O and extracted with Et2O (2×). The combined organic solution was washed (0.1 N HCl then brine), dried (MgSO4), filtered and concentrated. The crude benzaldehyde (16.9 g) was taken onto the next step without purification. 1H NMR was consistent with structure. Stirred at this temperature for 1 h stirred for 10 min extracted with Et2O (2×) The combined organic solution was washed (0.1 N HCl brine), dried (MgSO4) filtered concentrated The crude benzaldehyde (16.9 g) was taken onto the next step without purification