3-bromoazepan-2-one

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

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

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 3-bromoazepan-2-one (1.398 g, 7.28 mmol) in tetrahydrofuran (10 ml), was added sodium hydride (0.48 g, 12.00 mmol) at 0° C. The mixture was stirred at 0° C. for 1 hour, and 1-(bromomethyl)-4-methoxybenzene (1.610 g, 8.01 mmol) was added. The mixture was warmed to room temperature over the span of 2 hours. The reaction was quenched with saturated aqueous ammonium chloride and extracted with ethyl acetate. The organic phase was washed with brine, dried and concentrated to afford crude product, which was purified by chromatography on silica gel (ethyl acetate/hexanes=2/8) to afford 3-bromo-1-(4-methoxybenzyl)azepan-2-one (1.403 g, 4.49 mmol, 61.7% yield). MS ESI: [M+H]+ m/z 313.2. The mixture was warmed to room temperature over the span of 2 hours The reaction was quenched with saturated aqueous ammonium chloride extracted with ethyl acetate The organic phase was washed with brine dried concentrated to afford crude product, which was purified by chromatography on silica gel (ethyl acetate/hexanes=2/8)

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

Procedure: 54 g (1.0 mol) of sodium methylate and 144.6 g (1.0 mol) of 4-chlorothiophenol are initially introduced into 500 mL of methanol, and a methanolic solution of 192 g (1.0 mol) of α-bromocaprolactam is added dropwise at room temperature. After the exothermic reaction has ceased, the mixture is stirred for a further 3 hours at room temperature, the precipitated sodium bromide is then filtered off under suction and the mother liquor is evaporated down in vacuo. The precipitated crystals are filtered off under suction. After the exothermic reaction the precipitated sodium bromide is then filtered off under suction the mother liquor is evaporated down in vacuo The precipitated crystals are filtered off under suction

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

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 3-bromoazepan-2-one (1.398 g, 7.28 mmol) in tetrahydrofuran (10 ml), was added sodium hydride (0.48 g, 12.00 mmol) at 0° C. The mixture was stirred at 0° C. for 1 hour, and 1-(bromomethyl)-4-methoxybenzene (1.610 g, 8.01 mmol) was added. The mixture was warmed to room temperature over the span of 2 hours. The reaction was quenched with saturated aqueous ammonium chloride and extracted with ethyl acetate. The organic phase was washed with brine, dried and concentrated to afford crude product, which was purified by chromatography on silica gel (ethyl acetate/hexanes=2/8) to afford 3-bromo-1-(4-methoxybenzyl)azepan-2-one (1.403 g, 4.49 mmol, 61.7% yield). MS ESI: [M+H]+ m/z 313.2. The mixture was warmed to room temperature over the span of 2 hours The reaction was quenched with saturated aqueous ammonium chloride extracted with ethyl acetate The organic phase was washed with brine dried concentrated to afford crude product, which was purified by chromatography on silica gel (ethyl acetate/hexanes=2/8)

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

Procedure: A solution of 16 g (59 mmol) of 3,3-dibromoazacycloheptan-2-one, 150 ml of glacial acetic acid, 5.5 g (65 mmol) of sodium acetate, and 0.5 g of palladium on carbon (10%) was placed in a hydrogenator bottle and reduced under hydrogen at 30 psi. The mixture was filtered, and the filtrate distilled under vacuum to remove the acetic acid. The residue was neutralized with sat. Na2CO3, extracted into CH2Cl2, dried over MgSO4, and concentrated to yield 10.8 g (95%) of the product as an off-white solid; mp 109°-111° C.; NMR (CDCl3) 7.2 (1 H,m), 4.6 (1 H,m), 3.4 (2 H,m), 2.1 (4 H,m), 1.7 (2 H,m). The mixture was filtered the filtrate distilled under vacuum to remove the acetic acid extracted into CH2Cl2 dried over MgSO4 concentrated

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

Procedure: A benzene (50 g; manufactured by JUNSEI CHEMICAL Co., Ltd.) solution in which 240 g (1.5 mol) of bromine (manufactured by JUNSEI CHEMICAL Co., Ltd.) were dissolved was cooled with ice to 10° C. To the cooled solution, 450 g (1.6 mol) of 90% phosphorus tribromide (manufactured by Wako Pure Chemical Industries Ltd.) were added while the temperature of the reaction solution was maintained at 10° C. or less, and the resultant reaction solution was stirred for 60 minutes. Into the reaction solution, a benzene (220 g) solution in which 85 g (0.75 mol) of commercially available 6-hexanolactam (trade name: ε-caprolactam; manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved was added dropwise through a dropping funnel over 30 minutes while maintaining the temperature of the reaction solution at 10° C. or less. was maintained at 10° C. or less the resultant reaction solution was added dropwise through a dropping funnel over 30 minutes while maintaining the temperature of the reaction solution at 10° C. or less

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 3-bromoazepan-2-one (1.398 g, 7.28 mmol) in tetrahydrofuran (10 ml), was added sodium hydride (0.48 g, 12.00 mmol) at 0° C. The mixture was stirred at 0° C. for 1 hour, and 1-(bromomethyl)-4-methoxybenzene (1.610 g, 8.01 mmol) was added. The mixture was warmed to room temperature over the span of 2 hours. The reaction was quenched with saturated aqueous ammonium chloride and extracted with ethyl acetate. The organic phase was washed with brine, dried and concentrated to afford crude product, which was purified by chromatography on silica gel (ethyl acetate/hexanes=2/8) to afford 3-bromo-1-(4-methoxybenzyl)azepan-2-one (1.403 g, 4.49 mmol, 61.7% yield). MS ESI: [M+H]+ m/z 313.2. The mixture was warmed to room temperature over the span of 2 hours The reaction was quenched with saturated aqueous ammonium chloride extracted with ethyl acetate The organic phase was washed with brine dried concentrated to afford crude product, which was purified by chromatography on silica gel (ethyl acetate/hexanes=2/8)

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

Procedure: 54 g (1.0 mol) of sodium methylate and 144.6 g (1.0 mol) of 4-chlorothiophenol are initially introduced into 500 mL of methanol, and a methanolic solution of 192 g (1.0 mol) of α-bromocaprolactam is added dropwise at room temperature. After the exothermic reaction has ceased, the mixture is stirred for a further 3 hours at room temperature, the precipitated sodium bromide is then filtered off under suction and the mother liquor is evaporated down in vacuo. The precipitated crystals are filtered off under suction. After the exothermic reaction the precipitated sodium bromide is then filtered off under suction the mother liquor is evaporated down in vacuo The precipitated crystals are filtered off under suction

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

Procedure: 54 g (1.0 mol) of sodium methylate and 144.6 g (1.0 mol) of 4-chlorothiophenol are initially introduced into 500 mL of methanol, and a methanolic solution of 192 g (1.0 mol) of α-bromocaprolactam is added dropwise at room temperature. After the exothermic reaction has ceased, the mixture is stirred for a further 3 hours at room temperature, the precipitated sodium bromide is then filtered off under suction and the mother liquor is evaporated down in vacuo. The precipitated crystals are filtered off under suction. After the exothermic reaction the precipitated sodium bromide is then filtered off under suction the mother liquor is evaporated down in vacuo The precipitated crystals are filtered off under suction

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