1-(4-iodophenyl)ethanone

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

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

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

Procedure: In a manner similar to that describe in Example 434 a mixture of (S)-5-ethynyl-N-[methyl(oxo)phenyl-λ6-sulfanylidene]nicotinamide and 4-iodoacetophenone were reacted to give the title compound as a light yellow foam (52 mg, 86%). were reacted

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

Procedure: 7.8 g of 4-iodoacetophenone are converted into the pyridazinone in accordance with GWP 1.

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

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

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

Procedure: A solution of bromine (79.3 g, 508 mmol) in glacial acetic acid (50 mL) was added at room temperature to a solution of 1-(4-Iodo-phenyl)-ethanone (Aldrich, 125 g, 508 mmol) in glacial acetic acid (600 mL). The mixture was stirred for 10 h, then concentrated under reduced pressure and the residue was diluted with ethyl acetate (100 mL), and washed with brine (3×50 mL). The organic layer was concentrated, and the residue was crystallized from ethyl ether to provide the title compound as a yellow solid (150 g, 462 mmol, 91% yield). 1H NMR (300 MHz, CDCl3) δ 4.39 (s, 2H), 7.69 (d, J=8.5 Hz, 2H), 7.87 ppm (d, J=8.5 Hz, 2H); MS (DCl/NH3) m/z 246 (M−Br)+264 (M−Br+NH4)+. concentrated under reduced pressure the residue was diluted with ethyl acetate (100 mL) washed with brine (3×50 mL) The organic layer was concentrated the residue was crystallized from ethyl ether

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

Procedure: A solution of bromine (79.3 g, 508 mmol) in glacial acetic acid (50 mL) was added at room temperature to a solution of 1-(4-Iodo-phenyl)-ethanone (Aldrich, 125 g, 508 mmol) in glacial acetic acid (600 mL). The mixture was stirred for 10 h, then concentrated under reduced pressure and the residue was diluted with ethyl acetate (100 mL), and washed with brine (3×50 mL). The organic layer was concentrated, and the residue was crystallized from ethyl ether to provide the title compound as a yellow solid (150 g, 462 mmol, 91% yield). 1H NMR (300 MHz, CDCl3) δ 4.39 (s, 2H), 7.69 (d, J=8.5 Hz, 2H), 7.87 ppm (d, J=8.5 Hz, 2H); MS (DCl/NH3) m/z 246 (M−Br)+264 (M−Br+NH4)+. concentrated under reduced pressure the residue was diluted with ethyl acetate (100 mL) washed with brine (3×50 mL) The organic layer was concentrated the residue was crystallized from ethyl ether

Conditions: temp:15.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Dissolving 20 g (81 mmol) of 4′-iodo acetophenone into 200 milliliter of acetic acid, and adding 12.8 g (81 mmol) of bromine while cooling with ice, stirred at the temperature of 15° C. for 3 hours. After the color of bromine disappeared, adding water and separating the precipitated solids by filtration, thereby obtained 27 g of crude 2-bromo-4′-iodo acetophenone. while cooling with ice separating the precipitated solids by filtration

Conditions: temp:15.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Dissolving 20 g (81 mmol) of 4′-iodo acetophenone into 200 milliliter of acetic acid, and adding 12.8 g (81 mmol) of bromine while cooling with ice, stirred at the temperature of 15° C. for 3 hours. After the color of bromine disappeared, adding water and separating the precipitated solids by filtration, thereby obtained 27 g of crude 2-bromo-4′-iodo acetophenone. while cooling with ice separating the precipitated solids by filtration

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

Procedure: In a manner similar to that describe in Example 434 a mixture of (S)-5-ethynyl-N-[methyl(oxo)phenyl-λ6-sulfanylidene]nicotinamide and 4-iodoacetophenone were reacted to give the title compound as a light yellow foam (52 mg, 86%). were reacted

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

Procedure: Following General Procedure II, a mixture of KOSiMe3 (570 mg, 4.0 mmol, 2.0 equiv), (Z)-21 (379 mg, 2.2 mmol, 1.1 equiv), 4-iodoacetophenone (492 mg, 2.0 mmol) and Pd(dba2) (58 mg, 0.1 mmol, 0.05 equiv) was stirred at room temperature for 13 h, and then was filtered through SiO2. Purification by column chromatography (RP C18, MeOH/H2O, 9/1) and Kugelrohr distillation afforded 360 mg (83%) of (Z)-154c as colorless oil. was filtered through SiO2 Purification by column chromatography (RP C18, MeOH/H2O, 9/1) and Kugelrohr distillation afforded 360 mg (83%) of (Z)-154c as colorless oil