(2,6-dibromo-4-fluorophenyl)methanol

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

Procedure: To a solution of (2,6-dibromo-4-fluorophenyl)methanol (1041) (20 g, 71 mmol) in CH2Cl2 (500 mL) at 0° C. was added pyridine (8.4 g, 107 mmol) and acetyl chloride (8.3 g, 107 mmol). The mixture was stirred at room temperature for 5 h. TLC showed the start material disappeared. The reaction was evaporated in vacuum and the residue was purified by silica-gel column chromatography eluting with petroleum ether/ethyl acetate (from 50:1 to 20:1) to give 104m as a white solid (20 g, 87%). MS: [M-Oac]+ 267. 1H NMR (500 MHz, CDCl3) δ 7.36 (d, J=7.5, 2H), 5.38 (s, 2H), 2.10 (s, 3H) The reaction was evaporated in vacuum the residue was purified by silica-gel column chromatography eluting with petroleum ether/ethyl acetate (from 50:1 to 20:1)

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

Procedure: To a solution of 101i (20 g, 71 mmol) in CH2Cl2 (500 mL) at 0° C. was added pyridine (8.4 g, 107 mmol) and acetyl chloride (8.3 g, 107 mmol). The mixture was stirred at room temperature for 5 h. TLC showed the start material disappeared. The reaction was evaporated in vacuum and the residue was purified by silica-gel column chromatography eluting with petroleum ether/ethyl acetate (from 50:1 to 20:1) to give 101j as a white solid (20 g, 87%). MS: [M−Oac]+ 267. 1H NMR (500 MHz, CDCl3) δ 7.36 (d, J=7.5, 2H), 5.38 (s, 2H), 2.10 (s, 3H). The reaction was evaporated in vacuum the residue was purified by silica-gel column chromatography eluting with petroleum ether/ethyl acetate (from 50:1 to 20:1)

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

Procedure: To a solution of 101i (20 g, 71 mmol) in CH2Cl2 (500 mL) at 0° C. was added pyridine (8.4 g, 107 mmol) and acetyl chloride (8.3 g, 107 mmol). The mixture was stirred at room temperature for 5 h. TLC showed the start material disappeared. The reaction was evaporated in vacuum and the residue was purified by silica-gel column chromatography eluting with petroleum ether/ethyl acetate (from 50:1 to 20:1) to give 101j as a white solid (20 g, 87%). MS: [M−Oac]+ 267. 1H NMR (500 MHz, CDCl3) δ 7.36 (d, J=7.5, 2H), 5.38 (s, 2H), 2.10 (s, 3H). The reaction was evaporated in vacuum the residue was purified by silica-gel column chromatography eluting with petroleum ether/ethyl acetate (from 50:1 to 20:1)

Conditions: temp:10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 101h (20 g, 71 mmol) in EtOH (500 mL) was added NaBH4 (10 g, 284 mmol). The mixture was stirred at room temperature (10° C.) for 4 h and TLC showed the start material disappeared. The reaction was quenched by aqueous HCl solution (150 mL, 1M) and evaporated in vacuo until most of EtOH was distilled. The residue was extracted by ethyl acetate (500 mL×3). The organic layers were combined, dried with Na2SO4, and evaporated in vacuo. The residue was purified by silica-gel column chromatography eluting with petroleum ether/ethyl acetate (from 50:1 to 20:1) to give 101i as a white solid (15 g, 75%). MS: [M−OH]+ 267. 1H NMR (500 MHz, DMSO-d6) δ 7.68 (d, J=8.5, 2H), 5.23 (s, 1H), 4.71 (s, 2H). The reaction was quenched by aqueous HCl solution (150 mL, 1M) evaporated in vacuo until most of EtOH was distilled The residue was extracted by ethyl acetate (500 mL×3) dried with Na2SO4 evaporated in vacuo The residue was purified by silica-gel column chromatography eluting with petroleum ether/ethyl acetate (from 50:1 to 20:1)

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

Procedure: To a solution of (2,6-dibromo-4-fluorophenyl)methanol (104l) (20 g, 71 mmol) in CH2Cl2 (500 mL) at 0° C. was added pyridine (8.4 g, 107 mmol) and acetyl chloride (8.3 g, 107 mmol). The mixture was stirred at room temperature for 5 h. TLC showed the start material disappeared. The reaction was evaporated in vacuum and the residue was purified by silica-gel column chromatography eluting with petroleum ether/ethyl acetate (from 50:1 to 20:1) to give 104m as a white solid (20g, 87%). MS: [M-Oac]+ 267. 1H NMR (500 MHz, CDCl3) δ 7.36 (d, J=7.5, 2H), 5.38 (s, 2H), 2.10 (s, 3H) The reaction was evaporated in vacuum the residue was purified by silica-gel column chromatography eluting with petroleum ether/ethyl acetate (from 50:1 to 20:1)

Conditions: temp:10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 104k (20 g, 71 mmol) in EtOH (500 mL) was added NaBH4 (10 g, 284 mmol). The mixture was stirred at room temperature (10° C.) for 4 h and TLC showed the starting material had disappeared. The reaction was quenched by aqueous HCl solution (150 mL, 1M) and evaporated in vacuo until most of EtOH was distilled. The residue was extracted by ethyl acetate (500 mL×3). The organic layers were combined, dried with Na2SO4, and evaporated in vacuo. The residue was purified by silica-gel column chromatography eluting with petroleum ether/ethyl acetate (from 50:1 to 20:1) to give 104l as a white solid (15g, 75%). MS: [M-OH]+ 267. 1H NMR (500 MHz, DMSO-d6) δ 7.68 (d, J=8.5, 2H), 5.23 (s, 1H), 4.71 (s, 2H). The reaction was quenched by aqueous HCl solution (150 mL, 1M) evaporated in vacuo until most of EtOH was distilled The residue was extracted by ethyl acetate (500 mL×3) dried with Na2SO4 evaporated in vacuo The residue was purified by silica-gel column chromatography eluting with petroleum ether/ethyl acetate (from 50:1 to 20:1)

Conditions: temp:10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 104k (20 g, 71 mmol) in EtOH (500 mL) was added NaBH4 (10 g, 284 mmol). The mixture was stirred at room temperature (10° C.) for 4 h and TLC showed the starting material had disappeared. The reaction was quenched by aqueous HCl solution (150 mL, 1M) and evaporated in vacuo until most of EtOH was distilled. The residue was extracted by ethyl acetate (500 mL×3). The organic layers were combined, dried with Na2SO4, and evaporated in vacuo. The residue was purified by silica-gel column chromatography eluting with petroleum ether/ethyl acetate (from 50:1 to 20:1) to give 104l as a white solid (15g, 75%). MS: [M-OH]+ 267. 1H NMR (500 MHz, DMSO-d6) δ 7.68 (d, J=8.5, 2H), 5.23 (s, 1H), 4.71 (s, 2H). The reaction was quenched by aqueous HCl solution (150 mL, 1M) evaporated in vacuo until most of EtOH was distilled The residue was extracted by ethyl acetate (500 mL×3) dried with Na2SO4 evaporated in vacuo The residue was purified by silica-gel column chromatography eluting with petroleum ether/ethyl acetate (from 50:1 to 20:1)

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

Procedure: To a solution of 101i (20 g, 71 mmol) in CH2Cl2 (500 mL) at 0° C. was added pyridine (8.4 g, 107 mmol) and acetyl chloride (8.3 g, 107 mmol). The mixture was stirred at room temperature for 5 h. TLC showed the start material disappeared. The reaction was evaporated in vacuum and the residue was purified by silica-gel column chromatography eluting with petroleum ether/ethyl acetate (from 50:1 to 20:1) to give 101j as a white solid (20 g, 87%). MS: [M−Oac]+ 267. 1H NMR (500 MHz, CDCl3) δ 7.36 (d, J=7.5, 2H), 5.38 (s, 2H), 2.10 (s, 3H). The reaction was evaporated in vacuum the residue was purified by silica-gel column chromatography eluting with petroleum ether/ethyl acetate (from 50:1 to 20:1)

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

Procedure: To a solution of (2,6-dibromo-4-fluorophenyl)methanol (104l) (20 g, 71 mmol) in CH2Cl2 (500 mL) at 0° C. was added pyridine (8.4 g, 107 mmol) and acetyl chloride (8.3 g, 107 mmol). The mixture was stirred at room temperature for 5 h. TLC showed the start material disappeared. The reaction was evaporated in vacuum and the residue was purified by silica-gel column chromatography eluting with petroleum ether/ethyl acetate (from 50:1 to 20:1) to give 104m as a white solid (20 g, 87%). MS: [M-Oac]+ 267. 1H NMR (500 MHz, CDCl3) δ 7.36 (d, J=7.5, 2H), 5.38 (s, 2H), 2.10 (s, 3H) The reaction was evaporated in vacuum the residue was purified by silica-gel column chromatography eluting with petroleum ether/ethyl acetate (from 50:1 to 20:1)

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

Procedure: To a solution of (2,6-dibromo-4-fluorophenyl)methanol (1041) (20 g, 71 mmol) in CH2Cl2 (500 mL) at 0° C. was added pyridine (8.4 g, 107 mmol) and acetyl chloride (8.3 g, 107 mmol). The mixture was stirred at room temperature for 5 h. TLC showed the start material disappeared. The reaction was evaporated in vacuum and the residue was purified by silica-gel column chromatography eluting with petroleum ether/ethyl acetate (from 50:1 to 20:1) to give 104m as a white solid (20 g, 87%). MS: [M-Oac]+ 267. 1H NMR (500 MHz, CDCl3) δ 7.36 (d, J=7.5, 2H), 5.38 (s, 2H), 2.10 (s, 3H) The reaction was evaporated in vacuum the residue was purified by silica-gel column chromatography eluting with petroleum ether/ethyl acetate (from 50:1 to 20:1)

Conditions: temp:10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 101h (20 g, 71 mmol) in EtOH (500 mL) was added NaBH4 (10 g, 284 mmol). The mixture was stirred at room temperature (10° C.) for 4 h and TLC showed the start material disappeared. The reaction was quenched by aqueous HCl solution (150 mL, 1M) and evaporated in vacuo until most of EtOH was distilled. The residue was extracted by ethyl acetate (500 mL×3). The organic layers were combined, dried with Na2SO4, and evaporated in vacuo. The residue was purified by silica-gel column chromatography eluting with petroleum ether/ethyl acetate (from 50:1 to 20:1) to give 101i as a white solid (15 g, 75%). MS: [M−OH]+ 267. 1H NMR (500 MHz, DMSO-d6) δ 7.68 (d, J=8.5, 2H), 5.23 (s, 1H), 4.71 (s, 2H). The reaction was quenched by aqueous HCl solution (150 mL, 1M) evaporated in vacuo until most of EtOH was distilled The residue was extracted by ethyl acetate (500 mL×3) dried with Na2SO4 evaporated in vacuo The residue was purified by silica-gel column chromatography eluting with petroleum ether/ethyl acetate (from 50:1 to 20:1)

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

Procedure: To a solution of (2,6-dibromo-4-fluorophenyl)methanol (104l) (20 g, 71 mmol) in CH2Cl2 (500 mL) at 0° C. was added pyridine (8.4 g, 107 mmol) and acetyl chloride (8.3 g, 107 mmol). The mixture was stirred at room temperature for 5 h. TLC showed the start material disappeared. The reaction was evaporated in vacuum and the residue was purified by silica-gel column chromatography eluting with petroleum ether/ethyl acetate (from 50:1 to 20:1) to give 104m as a white solid (20g, 87%). MS: [M-Oac]+ 267. 1H NMR (500 MHz, CDCl3) δ 7.36 (d, J=7.5, 2H), 5.38 (s, 2H), 2.10 (s, 3H) The reaction was evaporated in vacuum the residue was purified by silica-gel column chromatography eluting with petroleum ether/ethyl acetate (from 50:1 to 20:1)