N-(3,4-dihydro-2H-naphthalen-1-ylidene)hydroxylamine

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:22.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of α-tetralone (100.0 g, 0.68 mol) in 300 mL of methanol was added hydroxylamine hydrochloride (71.0 g, 1.03 mol) and the resulting solution was stirred at reflux for 2 hours. The mixture was allowed to cool to 20-24° C. and was concentrated under reduced pressure. The resulting mixture was diluted with 1 L of water and extracted with dichloromethane. The organic layer was washed with saturated aqueous sodium chloride, dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was crystallized from isopropanol to provide 70.0 g (63%) of the desired compound as an off-white solid. at reflux for 2 hours was concentrated under reduced pressure The resulting mixture was diluted with 1 L of water extracted with dichloromethane The organic layer was washed with saturated aqueous sodium chloride dried over sodium sulfate filtered concentrated under reduced pressure The residue was crystallized from isopropanol

反応条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To 10 L of methanesulfonic acid in a 22 L 3-neck flask equipped with an overhead stirrer, a temperature probe, nitrogen inlet and reflux condenser was added 2.6 Kg (18.61 mol) of phosphorus pentoxide. An additional 1.6 L of methansulfonic acid was used to wash all the phosphorus pentoxide into the vessel. The mixture was heated at 90° C. for 2.5 hours then cooled to 50° C. using an ice bath and treated with 2.00 Kg (12.41 mol) of 1-tetralone oxime in several portions over 15 minutes. The mixture was heated at 63° C. for 10 minutes then slowly heated to 80° C. and kept at 80° C. for 3 hours. The reaction mixture was pumped into 70 L of ice then treated slowly with 11.25 L of 50% aqueous sodium hydroxide over 90 minutes at such a rate so as to maintain the temperature below 28° C. The mixture was filtered and 4 L of the filtrate was used to rinse the vessel. The wet cake (pink) was washed with 8 L of water then suction dried for 45 minutes then transferred to two trays and dried under vacuum at 40° C. for 2 days to give 1.9 Kg (11.79 mol, 95%) of product, 1H NMR (250 MHz, CDCl3): 2.24 (m, 2H), 2.38 (t, 6 Hz, 2H), 2.82 (t, 6 Hz, 2H), 7.03 (d, 8 Hz, 1H), 7.13 (m, 1H), 7.24 (m, 2H), 8.63 (br s, 1H). a temperature probe, nitrogen inlet and reflux condenser to wash all the phosphorus pentoxide into the vessel then cooled to 50° C. The mixture was heated at 63° C. for 10 minutes then slowly heated to 80° C. to maintain the temperature below 28° C The mixture was filtered to rinse the vessel The wet cake (pink) was washed with 8 L of water suction dried for 45 minutes dried under vacuum at 40° C. for 2 days

反応条件: temp:75.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To 4.6 L of water at room temperature in a 4-neck 50 L flask sitting in a steam bath apparatus equipped with an overhead stirrer, a temperature probe and reflux condenser was added 3.72 Kg (27.36 mol) of sodium acetate with stirring, followed by 1.9 Kg of hydroxylamine hydrochloride (27.36 mol). To this slurry at room temperature, 12 L of ethanol was added followed by 1.994 Kg (13.68 mol) of 1-tetralone. Additional ethanol (1.7 L) was used to rinse off the funnel and added to the reaction mixture. The resulting light orange slurry was heated to 75° C. over 40 minutes and maintained at 75°-85° C. for another 75 minutes. The reaction mixture was cooled with the aid of ice packed around the flask. When the internal temperature reached 32° C., the reaction mixture was pumped over 15 minutes into 60 L of ice contained in a 200 L vessel. The reaction vessel was washed with an additional 2 L of water which was added to the 200 L vessel. When the ice melted, the mixture was filtered through a filter pad and the wet cake washed with 4 L of water. The wet cake was suction dried for 1 hour then transferred to two trays and dried under vacuum at 40° C. for 2 days to give 2.094 Kg (13.01 mol, 95%) of product, 1H NMR (250 MHz, CDCl3): 1.90 (m, 2H), 2.80 (t, 6 Hz, 2H), 2.88 (t, 6 Hz, 2H), 7.15-7.35 (m, 3H), 7.90 (d, 8 Hz, 1H), 8.9 (br s, 1H). apparatus equipped with an overhead stirrer a temperature probe and reflux condenser to rinse off the funnel added to the reaction mixture maintained at 75°-85° C. for another 75 minutes The reaction mixture was cooled with the aid of ice reached 32° C. contained in a 200 L vessel The reaction vessel was washed with an additional 2 L of water which was added to the 200 L vessel the mixture was filtered through a filter pad the wet cake washed with 4 L of water dried for 1 hour dried under vacuum at 40° C. for 2 days

反応条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To 10 L of methanesulfonic acid in a 22 L 3-neck flask equipped with an overhead stirrer, a temperature probe, nitrogen inlet and reflux condenser was added 2.6 Kg (18.61 mol) of phosphorus pentoxide. An additional 1.6 L of methanesulfonic acid was used to wash wall the phosphorus pentoxide into the vessel. The mixture was heated at 90° C. for 2.5 hours then cooled to 50° C. using an ice bath and treated with 2.00 Kg (12.41 mol) of 1-tetralone oxime in several portions over 15 minutes. The mixture was heated at 63° C. for 10 minutes then slowly heated to 80° C. and kept at 80° C. for 3 hours. The reaction mixture was pumped into 70 L of ice then treated slowly with 11.25 L of 50% aqueous sodium hydroxide over 90 minutes at such a rate so as to maintain the temperature below 28° C. The mixture was filtered and 4 L of the filtrate was used to rinse the vessel. The wet cake (pink) was washed with 8 L of water then suction dried for 45 minutes then transferred to two trays and dried under vacuum at 40 ° C. for 2 days to give 1.9 Kg (11.79 mol, 95%) of product. 1H NMR (250 MHz,CDCl3): 2.24 (m,2H), 2.38 (t,6 Hz,2H), 2.82 (t,6 Hz,2H), 7.03 (d,8 Hz,1H), 7.13 (m,1H), 7.24 (m,2H), 8.63 (br s,1H). a temperature probe, nitrogen inlet and reflux condenser to wash wall the phosphorus pentoxide into the vessel then cooled to 50° C. The mixture was heated at 63° C. for 10 minutes then slowly heated to 80° C. to maintain the temperature below 28° C The mixture was filtered to rinse the vessel The wet cake (pink) was washed with 8 L of water suction dried for 45 minutes dried under vacuum at 40 ° C. for 2 days

反応条件: temp:75.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To 4.6 L of water at room temperature in a 4-neck 50 L flask stirring in a steam bath apparatus equipped with an overhead stirrer, a temperature probe and reflux condenser was added 3.72 Kg (27.36 mol) of sodium acetate with stirring, followed by 1.9 Kg of hydroxylamine hydrochloride (27.36 mol). To this slurry at room temperature, 12 L of ethanol was added followed by 1.994 Kg (13.68 mol) of 1-tetralone. Additional ethanol (1.7 L) was used to rinse off the funnel and added to the reaction mixture. The resulting light orange slurry was heated to 75° C. over 40 minutes and maintained at 75°-85° C. for another 75 minutes. The reaction mixture was cooled with the aid of ice packed around the flask. When the internal temperature reached 32° C., the reaction mixture was pumped over 15 minutes into 60 L of ice contained in a 200 L vessel. The reaction vessel was washed with an additional 12 L of water which was added to the 200 L vessel. When the ice melted, the mixture was filtered through a filter pad and the wet cake washed with 4 L of water. The wet cake was suction dried for 1 hour then transferred to two trays and dried under vacuum at 40` C. for 2 days to give 2.094 Kg (13.01 mol, 95%) of product. 1H NMR (250 MHz,CDCl3): 1.90 (m,2H), 2.80 (t,6 Hz,2H), 2.88 (t,6 Hz,2H), 7.15-7.35 (m,3H), 7.90 (d,8 Hz,1H), 8.9 (br s,1H). equipped with an overhead stirrer a temperature probe and reflux condenser to rinse off the funnel added to the reaction mixture maintained at 75°-85° C. for another 75 minutes The reaction mixture was cooled with the aid of ice reached 32° C. contained in a 200 L vessel The reaction vessel was washed with an additional 12 L of water which was added to the 200 L vessel the mixture was filtered through a filter pad the wet cake washed with 4 L of water dried for 1 hour dried under vacuum at 40` C

反応条件: temp:75.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To 4.6 L of water at room temperature in a 4-neck 50 L flask stirring in a steam bath apparatus equipped with an overhead stirrer, a temperature probe and reflux condenser was added 3.72 Kg (27.36 mol) of sodium acetate with stirring, followed by 1.9 Kg of hydroxylamine hydrochloride (27.36 mol). To this slurry at room temperature, 12 L of ethanol was added followed by 1.994 Kg (13.68 mol) of 1-tetralone. Additional ethanol (1.7 L) was used to rinse off the funnel and added to the reaction mixture. The resulting light orange slurry was heated to 75° C. over 40 minutes and maintained at 75°-85° C. for another 75 minutes. The reaction mixture was cooled with the aid of ice packed around the flask. When the internal temperature reached 32° C., the reaction mixture was pumped over 15 minutes into 60 L of ice contained in a 200 L vessel. The reaction vessel was washed with an additional 12 L of water which was added to the 200 L vessel. When the ice melted, the mixture was filtered through a filter pad and the wet cake washed with 4 L of water. The wet cake was suction dried for 1 hour then transferred to two trays and dried under vacuum at 40` C. for 2 days to give 2.094 Kg (13.01 mol, 95%) of product. 1H NMR (250 MHz,CDCl3): 1.90 (m,2H), 2.80 (t,6 Hz,2H), 2.88 (t,6 Hz,2H), 7.15-7.35 (m,3H), 7.90 (d,8 Hz,1H), 8.9 (br s,1H). equipped with an overhead stirrer a temperature probe and reflux condenser to rinse off the funnel added to the reaction mixture maintained at 75°-85° C. for another 75 minutes The reaction mixture was cooled with the aid of ice reached 32° C. contained in a 200 L vessel The reaction vessel was washed with an additional 12 L of water which was added to the 200 L vessel the mixture was filtered through a filter pad the wet cake washed with 4 L of water dried for 1 hour dried under vacuum at 40` C

反応条件: temp:22.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of α-tetralone (100.0 g, 0.68 mol) in 300 mL of methanol was added hydroxylamine hydrochloride (71.0 g, 1.03 mol) and the resulting solution was stirred at reflux for 2 hours. The mixture was allowed to cool to 20-24° C. and was concentrated under reduced pressure. The resulting mixture was diluted with 1 L of water and extracted with dichloromethane. The organic layer was washed with saturated aqueous sodium chloride, dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was crystallized from isopropanol to provide 70.0 g (63%) of the desired compound as an off-white solid. at reflux for 2 hours was concentrated under reduced pressure The resulting mixture was diluted with 1 L of water extracted with dichloromethane The organic layer was washed with saturated aqueous sodium chloride dried over sodium sulfate filtered concentrated under reduced pressure The residue was crystallized from isopropanol

反応条件: temp:22.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of α-tetralone (100.0 g, 0.68 mol) in 300 mL of methanol was added hydroxylamine hydrochloride (71.0 g, 1.03 mol) and the resulting solution was stirred at reflux for 2 hours. The mixture was allowed to cool to 20-24° C. and was concentrated under reduced pressure. The resulting mixture was diluted with 1 L of water and extracted with dichloromethane. The organic layer was washed with saturated aqueous sodium chloride, dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was crystallized from isopropanol to provide 70.0 g (63%) of the desired compound as an off-white solid. at reflux for 2 hours was concentrated under reduced pressure The resulting mixture was diluted with 1 L of water extracted with dichloromethane The organic layer was washed with saturated aqueous sodium chloride dried over sodium sulfate filtered concentrated under reduced pressure The residue was crystallized from isopropanol

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

実験手順: A solution of 7-methoxy-1-tetralone (10 g; 56.8 mmol) in pyridine (28 ml) and hydroxylamine hyrochloride (9 g; 130.6 mmol) was refluxed for 12 hours. The mixture was poured into water and extracted with CH2Cl2. The organic phase was washed with 1N HCl and 0.5N NaHC3, dried over MgSO4 and evaporated to give 7-methoxy-,1,2,3,4-tetrahydronaphthalen-1-one oxime as a brown solid (10 g; 92.5%). extracted with CH2Cl2 The organic phase was washed with 1N HCl and 0.5N NaHC3 dried over MgSO4 evaporated

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

実験手順: A solution of 7-methoxy-1-tetralone (10 g; 56.8 mmol) in pyridine (28 ml) and hydroxylamine hyrochloride (9 g; 130.6 mmol) was refluxed for 12 hours. The mixture was poured into water and extracted with CH2Cl2. The organic phase was washed with 1N HCl and 0.5N NaHC3, dried over MgSO4 and evaporated to give 7-methoxy-,1,2,3,4-tetrahydronaphthalen-1-one oxime as a brown solid (10 g; 92.5%). extracted with CH2Cl2 The organic phase was washed with 1N HCl and 0.5N NaHC3 dried over MgSO4 evaporated

反応条件: temp:22.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Add hydroxylamine hydrochloride (71.0 g, 1.03 mol) to a solution of α-tetralone (100.0 g, 0.68 mol) in 300 mL of methanol and stir the resulting solution at reflux for 2 hours. Cool the mixture to 20-24° C. and concentrate under reduced pressure. Dilute the residue with 1 L of water and extract with dichloromethane. Wash the organic layer with saturated aqueous sodium chloride, dry over sodium sulfate, filter, and concentrate under reduced pressure. Crystallize the residue from isopropanol to provide the desired compound as an off-white solid (70.0 g, 63%). at reflux for 2 hours concentrate under reduced pressure Dilute the residue with 1 L of water extract with dichloromethane Wash the organic layer with saturated aqueous sodium chloride dry over sodium sulfate filter concentrate under reduced pressure Crystallize the residue from isopropanol