1,2,3,5-tetrahydro-3-benzazepin-4-one

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: To a slurry of sodium hydride (1.1 eq) in 15 mL of dry DMF was added 2,3,4,5-tetrahydro-1H-3-benzazepin-2-one (0.0042 moles) as a solution in 10 mL of DMF. Methyl iodide (about 2 eq.) was then added. When complete by TLC, the reaction mixture was poured over ice and extracted into ethyl acetate. The organic layer was washed with water, followed by brine. The organic layer was then dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by HPLC (LC 2000), eluting with an ethyl acetate/hexane system to give 3-methyl-2,3,4,5-tetrahydro-1H-3-benzazepin-2-one. When complete by TLC, the reaction mixture was poured over ice extracted into ethyl acetate The organic layer was washed with water The organic layer was then dried over Na2SO4 filtered concentrated under reduced pressure The residue was purified by HPLC (LC 2000) eluting with an ethyl acetate/hexane system

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

実験手順: To a slurry of sodium hydride (1.1 eq) in 15 mL of dry DMF was added 2,3,4,5-tetrahydro-1H-3-benzazepin-2-one (0.0042 moles) as a solution in 10 mL of DMF. Methyl iodide (about 2 eq.) was then added. When complete by TLC, the reaction mixture was poured over ice and extracted into ethyl acetate. The organic layer was washed with water, followed by brine. The organic layer was then dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by HPLC (LC 2000), eluting with an ethyl acetate/hexane system to give 3-methyl-2,3,4,5-tetrahydro-1H-3-benzazepin-2-one. When complete by TLC, the reaction mixture was poured over ice extracted into ethyl acetate The organic layer was washed with water The organic layer was then dried over Na2SO4 filtered concentrated under reduced pressure The residue was purified by HPLC (LC 2000) eluting with an ethyl acetate/hexane system

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

実験手順: To a slurry of sodium hydride (1.1 eq) in 15 mL of dry DMF was added 2,3,4,5-tetrahydro-1H-3-benzazepin-2-one (0.0042 moles) as a solution in 10 mL of DMF. Methyl iodide (about 2 eq.) was then added. When complete by TLC, the reaction mixture was poured over ice and extracted into ethyl acetate. The organic layer was washed with water, followed by brine. The organic layer was then dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by HPLC (LC 2000), eluting with an ethyl acetate/hexane system to give 3-methyl-2,3,4,5-tetrahydro-1H-3-benzazepin-2-one. When complete by TLC, the reaction mixture was poured over ice extracted into ethyl acetate The organic layer was washed with water The organic layer was then dried over Na2SO4 filtered concentrated under reduced pressure The residue was purified by HPLC (LC 2000) eluting with an ethyl acetate/hexane system

反応条件: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: While maintaining the temperature of the reaction mixture below 65° C., NaN3 (13.35 g; 205.2 mmol) is added in small portions to a solution, heated beforehand to 55° C., of β-tetralone (25 g; 171 mmol) in a mixture of 150 ml of glacial acetic acid and concentrated sulphuric acid (33.39 g; 342 mmol; 18.25 ml). Stirring is then carried out for 8 hours at 70° C. After returning to ambient temperature, the reaction mixture is poured onto ice and diluted with ethyl acetate. After extracting the organic phase, drying over magnesium sulphate and concentrating, the residue obtained is purified by chromatography on silica gel (eluant ethyl acetate) to yield the expected compound. is added in small portions to a solution After returning to ambient temperature the reaction mixture is poured onto ice After extracting the organic phase drying over magnesium sulphate concentrating the residue obtained is purified by chromatography on silica gel (eluant ethyl acetate)

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 4,5-dihydro-1H-benzo[d]azepin-2(3H)-one (3.5 mmol) was in THF (25 mL) was stirred at 0° C. for 5 min. A solution of 1M BH3.THF (4 mL) was added dropwise to the reaction mixtureat 0° C. over a period of 30 min. The ice bath was removed and the reaction stirred at RT for 30 min. The reaction mixture was heated at 60° C. overnight, then cooled to 0° C. and additional 1M BH3.THF (2.5 mL) was added dropwise into the reaction mixtureat 0° C. over a period of 15 min. The ice bath was removed and it was stirred at RT for 30 min then heated at 60° C. for 7 h. The reaction mixture was cooled to RT, then further cooled with an ice-bath. The reaction was quenched by the addition of 2M HCl (15 mL). The mixture was heated for 30 min and then 20% NaOH (7.5 mL) was added with ice cooling. The solution was extracted with chloroform (3×) and the organic layer was washed with H2O. The organic layer was dried (Na2SO4), concentrated and redissolved in 2 mL of EtOAc and acidified with 3M HCl/EtOAc. The solid was filtered and dried under vacuum to obtain 2,3,4,5-tetrahydro-1H-benzo[d]azepine as a shiny powder (0.36 g, 69% yield). LC-MS (EI) m/z: 148.2 (M+H+). The ice bath was removed the reaction stirred at RT for 30 min The reaction mixture was heated at 60° C. overnight cooled to 0° C. additional 1M BH3.THF (2.5 mL) was added dropwise into the reaction mixtureat 0° C. over a period of 15 min The ice bath was removed it was stirred at RT for 30 min then heated at 60° C. for 7 h The reaction mixture was cooled to RT further cooled with an ice-bath The reaction was quenched by the addition of 2M HCl (15 mL) The mixture was heated for 30 min 20% NaOH (7.5 mL) was added with ice cooling The solution was extracted with chloroform (3×) the organic layer was washed with H2O The organic layer was dried (Na2SO4) concentrated redissolved in 2 mL of EtOAc The solid was filtered dried under vacuum

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

実験手順: beta-Tetralone (34 mmol) was suspended in 300 mL of 85% H3PO4 and treated portion wise with NaN3 (68 mmol) with vigorous stirring over a period of 1 h. During this time the reaction mixture was brought slowly to about 70° C. After stirring for a further 2 h at 70° C., no more N2 evolution was observed. The reaction mixture was cooled to RT, then poured into cold H2O (400 mL) and extracted with CHCl3 (3×). The organic layer was dried (MgSO4), concentrated and the residue was dissolved in EtOAc and the solid was filtered and washed with EtOAc to yield 4,5-dihydro-1H-benzo[d]azepin-2(3H)-one as a white solid (20% yield) along with a varying amount of the other region isomer 1,2,4,5-tetrahydrobenzo[c]azepin-3-one. was brought slowly to about 70° C After stirring for a further 2 h at 70° C. extracted with CHCl3 (3×) The organic layer was dried (MgSO4) concentrated the residue was dissolved in EtOAc the solid was filtered washed with EtOAc