4-(chloromethyl)benzaldehyde

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 40 mg of 2-mercapto-5-nitropyridine was added 200 mL of acetone, and the solution was stirred while cooled with water. To this reaction solution were added 43.6 of 4-chloromethylbenzaldehyde and 45 g of potassium carbonate, to conduct reaction. After the completion of the reaction, 1 L of water was added to the solution. The precipitated crystal was collected by filtration, washed with water, washed with methanol, and dried (yield amount 65.5 g, and yield 93.3%). reaction was added to the solution The precipitated crystal was collected by filtration washed with water washed with methanol dried (yield amount 65.5 g, and yield 93.3%)

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

実験手順: To 40 mg of 2-mercapto-5-nitropyridine was added 200 mL of acetone, and the solution was stirred while cooled with water. To this reaction solution were added 43.6 of 4-chloromethylbenzaldehyde and 45 g of potassium carbonate, to conduct reaction. After the completion of the reaction, 1 L of water was added to the solution. The precipitated crystal was collected by filtration, washed with water, washed with methanol, and dried (yield amount 65.5 g, and yield 93.3%). reaction was added to the solution The precipitated crystal was collected by filtration washed with water washed with methanol dried (yield amount 65.5 g, and yield 93.3%)

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

実験手順: 20 g (0.132 moles) of 90 percent pure 4-hydroxymethylbenzaldehyde were stirred for 2 hours at 80° C. under an argon atmosphere with 50 ml of 37 percent HCl (0.58 moles) and 200 ml of toluene. After cooling to room temperature, the aqueous phase was separated off and the toluene phase was evaporated in vacuo. This gave 16.2 g of crude product which, according to NMR, contained 78.8% by weight of 4-chloromethylbenzaldehyde, 10% by weight of 1,4-bis-chloromethylbenzene and 11.2% by weight of an unknown substance. A 4-chloromethylbenzaldehyde yield of 12.8 g, corresponding to 62.5% of the theoretical yield was calculated from the NMR result. the aqueous phase was separated off the toluene phase was evaporated in vacuo

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Hydroxylamine hydrochloride (10.11 g, 145.5 mmol) was added to a solution of 4-(chloromethyl)benzaldehyde 4 (7.5 g, 48.51 mmol) in EtOH. The mixture was heated at 50° C. for 3 h then concentrated in vacuo. The residue was partitioned between DCM and water. The combined organic extract was dried (MgSO4) and concentrated in vacuo yielding a white solid that was used without further purification (8.1 g, 98%). 1H NMR (400 MHz, DMSO) d 4.77 (2H, s), 7.46 (2H, d, J=8.0 Hz), 7.60 (2H, d, J=8.0 Hz), 8.15 (1H, s), 11.32 (1H, s). then concentrated in vacuo The residue was partitioned between DCM and water The combined organic extract was dried (MgSO4) concentrated in vacuo yielding a white solid that was used without further purification (8.1 g, 98%)

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 4-Chloromethylbenzaldehyde (11.93 g, 77.17 mmol) was dissolved in ethanol (200 ml), hydroxylamine hydrochloride (10.73 g, 154.41 mmol) was added, and the mixture was stirred at 50° C. for 3 hours. Ethanol was evaporated under reduced pressure, water was added, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure to give the title compound (12.69 g, 97%). Ethanol was evaporated under reduced pressure, water was added the mixture was extracted with ethyl acetate The extract was washed with saturated brine dried over anhydrous sodium sulfate The solvent was evaporated under reduced pressure

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

実験手順: Under an argon atmosphere, 4-chloromethylbenzoic acid (15.08 g, 88.40 mmol) was dissolved in THF (150 ml), and 1M borane-THF complex (135 ml, 135.00 mmol) was slowly added dropwise under ice-cooling. The mixture was stirred at room temperature for 2 hours, 1N sulfuric acid (160 ml) was added, and the mixture was stirred for 1 hour and extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and the obtained crude product was dissolved in dichloromethane (300 ml). Manganese dioxide (76.94 g, 885.0 mmol) was added, and the mixture was stirred overnight at room temperature. After filtration through celite, the filtrate was concentrated under reduced pressure to give the title compound (11.93 g, 87%). 1M borane-THF complex (135 ml, 135.00 mmol) was slowly added dropwise under ice- cooling the mixture was stirred for 1 hour extracted with ethyl acetate The organic layer was washed with saturated brine dried over anhydrous sodium sulfate The solvent was evaporated under reduced pressure the obtained crude product the mixture was stirred overnight at room temperature After filtration through celite the filtrate was concentrated under reduced pressure

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Hydroxylamine hydrochloride (10.11 g, 145.5 mmol) was added to a solution of 4-(chloromethyl)benzaldehyde 4 (7.5 g, 48.51 mmol) in EtOH. The mixture was heated at 50° C. for 3 h then concentrated in vacuo. The residue was partitioned between DCM and water. The combined organic extract was dried (MgSO4) and concentrated in vacuo yielding a white solid that was used without further purification (8.1 g, 98%). 1H NMR (400 MHz, DMSO) δ 4.77 (2H, s), 7.46 (2H, d, J=8.0 Hz), 7.60 (2H, d, J=8.0 Hz), 8.15 (1H, s), 11.32 (1H, s). then concentrated in vacuo The residue was partitioned between DCM and water The combined organic extract was dried (MgSO4) concentrated in vacuo yielding a white solid that was used without further purification (8.1 g, 98%)

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

実験手順: To 40 mg of 2-mercapto-5-nitropyridine was added 200 mL of acetone, and the solution was stirred while cooled with water. To this reaction solution were added 43.6 of 4-chloromethylbenzaldehyde and 45 g of potassium carbonate, to conduct reaction. After the completion of the reaction, 1 L of water was added to the solution. The precipitated crystal was collected by filtration, washed with water, washed with methanol, and dried (yield amount 65.5 g, and yield 93.3%). reaction was added to the solution The precipitated crystal was collected by filtration washed with water washed with methanol dried (yield amount 65.5 g, and yield 93.3%)

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

実験手順: 20 g (0.132 moles) of 90 percent pure 4-hydroxymethylbenzaldehyde were stirred for 2 hours at 80° C. under an argon atmosphere with 50 ml of 37 percent HCl (0.58 moles) and 200 ml of toluene. After cooling to room temperature, the aqueous phase was separated off and the toluene phase was evaporated in vacuo. This gave 16.2 g of crude product which, according to NMR, contained 78.8% by weight of 4-chloromethylbenzaldehyde, 10% by weight of 1,4-bis-chloromethylbenzene and 11.2% by weight of an unknown substance. A 4-chloromethylbenzaldehyde yield of 12.8 g, corresponding to 62.5% of the theoretical yield was calculated from the NMR result. the aqueous phase was separated off the toluene phase was evaporated in vacuo

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Hydroxylamine hydrochloride (10.11 g, 145.5 mmol) was added to a solution of 4-(chloromethyl)benzaldehyde 4 (7.5 g, 48.51 mmol) in EtOH. The mixture was heated at 50° C. for 3 h then concentrated in vacuo. The residue was partitioned between DCM and water. The combined organic extract was dried (MgSO4) and concentrated in vacuo yielding a white solid that was used without further purification (8.1 g, 98%). 1H NMR (400 MHz, DMSO) d 4.77 (2H, s), 7.46 (2H, d, J=8.0 Hz), 7.60 (2H, d, J=8.0 Hz), 8.15 (1H, s), 11.32 (1H, s). then concentrated in vacuo The residue was partitioned between DCM and water The combined organic extract was dried (MgSO4) concentrated in vacuo yielding a white solid that was used without further purification (8.1 g, 98%)