1-(2-bromophenyl)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:

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: To a suspension of methyltriphenyl phosphonium bromide (108 g, 303 mmol) in THF (750 mL) at room temperature was added KOtBu (112.24 g, 303 mmol) in portions. After being stirred for 5 min, the reaction mixture was treated with 2′bromoacetophenone (50.3 g, 253 mmol). The reaction mixture was stirred for 3 hrs at room temperature then quenched with saturated ammonium chloride. Extracted 3× with Et2O and the combined organic layers were washed with brine, dried over MgSO4 and evaporated under vacuum. Purified by silica gel chromatography (100% petroleum ether) to give 43.8 g (88%) of 1-bromo-2-(prop-1-en-2-yl)benzene as a colorless oil. The reaction mixture was stirred for 3 hrs at room temperature then quenched with saturated ammonium chloride Extracted 3× with Et2O the combined organic layers were washed with brine dried over MgSO4 evaporated under vacuum Purified by silica gel chromatography (100% petroleum ether)

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

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

Procedure: Prepared from 4-methylphenyltrimethylstannane (Example 69, Step A) and 2'-bromoacetophenone by the procedure described in Example 69, Step B. 1H NMR (200 MHz,CDCl3): 1.98 (s,3H), 2.37 (s,3H), 7.20 (s,4H), 7.3-7.5 (m,4H). FAB-MS: calculated for C15H14O 210; found 211 (M+H,100%).

Conditions: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 2′-bromoacetophenone (1.6 mL, 12 mmol), sodium hydrogencarbonate (2.5 g, 30 mmol), vinylboronic acid pinacol ester (3.0 mL, 18 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.69 g, 0.60 mmol) in a mixed solvent (50 mL), which consists of water and 1,4-dioxane (1:4), was stirred at 95° C. for 2.5 hours. Water (100 mL) was added to the reaction solution and extracted with ethyl acetate (100 mL). The organic layer was washed with brine (50 mL), dried over anhydrous magnesium sulfate. After the organic layer was filtered with celite and the solvent was removed under reduced pressure, the residue was purified by silica gel column chromatography to give the title reference compound (1.2 g) as an orange oil (Yield 69%). extracted with ethyl acetate (100 mL) The organic layer was washed with brine (50 mL) dried over anhydrous magnesium sulfate After the organic layer was filtered with celite the solvent was removed under reduced pressure the residue was purified by silica gel column chromatography

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

Procedure: 2'-Bromoacetophenone(0.1 moles, 20.0 g) was reacted with sodium mothoxide (0.13 moles) in 150 ml methanol and treated with Gold's Reagent (0.13 moles, 21.2 g) according to the procedure in J. Org, Chem, 45: 4525 (1988). The intermediate was purified by chromatography over silica gel eluted with 75-100% ethyl acetate in hexane. The resulting amine was dissolved in ethanol with 1,1-bis(methylthio)-2-nitroethylene (0.074 moles, 12.3 g) and sodium acetate (22.5 g) and refluxed for two hours. An additional 45 g of sodium acetate was added. The solution continued to reflux for 16 hours. The reaction was concentrated. Ethyl acetate and water were added. The organic phase was dried and evaporated. The product was chromatographed over silica gel eluted with a gradient of 25-100% ethyl acetate in hexane to yield 2.6 g of 2-amino-6-(2-bromophenyl)-3-nitropyridine. (MS) The intermediate was purified by chromatography over silica gel eluted with 75-100% ethyl acetate in hexane refluxed for two hours to reflux for 16 hours The reaction was concentrated Ethyl acetate and water were added The organic phase was dried evaporated The product was chromatographed over silica gel eluted with a gradient of 25-100% ethyl acetate in hexane

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

Procedure: 2'-Bromoacetophenone(0.1 moles, 20.0 g) was reacted with sodium mothoxide (0.13 moles) in 150 ml methanol and treated with Gold's Reagent (0.13 moles, 21.2 g) according to the procedure in J. Org, Chem, 45: 4525 (1988). The intermediate was purified by chromatography over silica gel eluted with 75-100% ethyl acetate in hexane. The resulting amine was dissolved in ethanol with 1,1-bis(methylthio)-2-nitroethylene (0.074 moles, 12.3 g) and sodium acetate (22.5 g) and refluxed for two hours. An additional 45 g of sodium acetate was added. The solution continued to reflux for 16 hours. The reaction was concentrated. Ethyl acetate and water were added. The organic phase was dried and evaporated. The product was chromatographed over silica gel eluted with a gradient of 25-100% ethyl acetate in hexane to yield 2.6 g of 2-amino-6-(2-bromophenyl)-3-nitropyridine. (MS) The intermediate was purified by chromatography over silica gel eluted with 75-100% ethyl acetate in hexane refluxed for two hours to reflux for 16 hours The reaction was concentrated Ethyl acetate and water were added The organic phase was dried evaporated The product was chromatographed over silica gel eluted with a gradient of 25-100% ethyl acetate in hexane

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

Procedure: Bromine (40.3 g, 0.25 mol) was added dropwise to a solution of 2′-Bromoacetophenone (50.0 g, 0.25 mol) in acetic acid (500 ml) over 1.5 hours at 15-20° C. The solution was then allowed to warm to room temperature and concentrated under reduced pressure to yield a crude product that was used without further purification. concentrated under reduced pressure