1-(2-bromophenyl)-N-methylmethanamine

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 2-bromo-N-methyl benzylamine (CAS#698-19-1, 0.57 mL, 3.89 mmol) in THF (10 mL) at 0° C. is added triethylamine (0.98 mL, 1.03 mmol) followed by acetoxyacetylchloride (0.63 mL, 5.86 mmol). The reaction is permitted to warm to room temperature and after two hours the reaction is quenched with saturated aqueous NaHCO3 and diluted with ethyl acetate. The layers are separated and the organic layer is dried with Na2SO4, filtered, and concentrated. The resulting residue is purified by silica gel flash chromatography (ethyl acetate-hexanes, 1:4 to 3:2) to provide acetic acid [(2-bromo-benzyl)-methyl-carbamoyl]-methyl ester; MS: (ESI) m/z 300.1, 302.1 (M+H)+. is quenched with saturated aqueous NaHCO3 diluted with ethyl acetate The layers are separated the organic layer is dried with Na2SO4 filtered concentrated The resulting residue is purified by silica gel flash chromatography (ethyl acetate-hexanes, 1:4 to 3:2)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 29.4 g of o-Bromobenzaldehyde and 81 ml of aqueous, 40% methylamine solution are combined with 238 ml of THF and at RT 19 g of NaBH4 are added in batches within 25 minutes. The mixture is left to stand overnight at RT, concentrated using a rotary evaporator, and the residue is stirred into ice water. The aqueous phase is extracted twice with ether and the combined ether phases are evaporated down under reduced pressure. After chromatography on silica gel with ethyl acetate or ethyl acetate/methanol (4:1) as eluant, 18.5 g of N-methyl-2-bromobenzylamine (a) are obtained in the form of a yellowish liquid. Yield: 58%. are added in batches within 25 minutes The mixture is left concentrated a rotary evaporator The aqueous phase is extracted twice with ether the combined ether phases are evaporated down under reduced pressure

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 2-bromobenzylamine (9 g, 36.1 mmol) in MeOH (60 ml) was added dropwise over 30 min. to a solution of methylamine in MeOH (200 mL of a 2.0 M solution, 0.4 mol). The resulting solution was stirred at rt for 2 h and concentrated. The residue obtained was dissolved in DCM (100 mL) and successively washed with saturated aqueous sodium carbonate, dried over sodium sulphate, and concentrated. The resulting oil was distilled to afford the title compound (7 g, 95%) as a colorless oil (b.p. 110° C. at 0.1 mm Hg, LC/MS retention time=1.22 min.; M+=201.92 Column: Phenominex 4.6 mm×50 mm. Solvent A=10% MeOH, 90% H2O, 10 mM NH4Ac; Solvent B=90% MeOH, 10% H2O, 10 nM NH4Ac, Flow rate: 4 mL/min, Gradient: 0% B-100% B 4 min.). concentrated The residue obtained successively washed with saturated aqueous sodium carbonate dried over sodium sulphate concentrated The resulting oil was distilled