(NE)-N-(1-phenylpropylidene)hydroxylamine

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: Diisopropylamine (21 mL, 148 mmol) was added to 50 mL of THF and cooled with an external ice bath. Butyllithium (56 mL, 141 mmol, 2.5 M in hexanes) was added and the mixture was stirred at 0° C. for 30 min, and brought to room temperature. The resulting LDA solution was added to a mixture of 1-phenyl-propan-1-one oxime (10 g, 67 mmol) and THF (50 mL) at 0° C. Following the addition, the reaction mixture was stirred at 0° C. for 1 hour and warmed to room temperature. The mixture was then transferred to a syringe and added dropwise to a flask containing a pre-cooled mixture of diethyl oxalate (46 mL, 336 mmol) and THF (150 mL) at 0° C. After the addition was complete, the reaction mixture was stirred at room temperature for 18 hours. The mixture was cooled in an ice bath and quenched with 150 mL of 3M hydrochloric acid. The organic layer was separated and the aqueous layer was extracted with EtOAc. The aqueous layer was then neutralized with solid sodium bicarbonate and extracted further with CH2Cl2. The organic layers were combined, dried over MgSO4 and concentrated. The crude oil was purified by chromatography (0-40% EtOAc/hexanes) to give 22 g of the title compound. MS: (+) m/z 250.48 (M+1). cooled with an external ice bath brought to room temperature the addition the reaction mixture was stirred at 0° C. for 1 hour warmed to room temperature The mixture was then transferred to a syringe added dropwise to a flask containing After the addition the reaction mixture was stirred at room temperature for 18 hours The mixture was cooled in an ice bath quenched with 150 mL of 3M hydrochloric acid The organic layer was separated the aqueous layer was extracted with EtOAc extracted further with CH2Cl2 dried over MgSO4 concentrated The crude oil was purified by chromatography (0-40% EtOAc/hexanes)

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

Procedure: Diisopropylamine (21 mL, 148 mmol) was added to 50 mL of THF and cooled with an external ice bath. Butyllithium (56 mL, 141 mmol, 2.5 M in hexanes) was added and the mixture was stirred at 0° C. for 30 min, and brought to room temperature. The resulting LDA solution was added to a mixture of 1-phenyl-propan-1-one oxime (10 g, 67 mmol) and THF (50 mL) at 0° C. Following the addition, the reaction mixture was stirred at 0° C. for 1 hour and warmed to room temperature. The mixture was then transferred to a syringe and added dropwise to a flask containing a pre-cooled mixture of diethyl oxalate (46 mL, 336 mmol) and THF (150 mL) at 0° C. After the addition was complete, the reaction mixture was stirred at room temperature for 18 hours. The mixture was cooled in an ice bath and quenched with 150 mL of 3M hydrochloric acid. The organic layer was separated and the aqueous layer was extracted with EtOAc. The aqueous layer was then neutralized with solid sodium bicarbonate and extracted further with CH2Cl2. The organic layers were combined, dried over MgSO4 and concentrated. The crude oil was purified by chromatography (0-40% EtOAc/hexanes) to give 22 g of the title compound. MS: (+) m/z 250.48 (M+1). cooled with an external ice bath brought to room temperature the addition the reaction mixture was stirred at 0° C. for 1 hour warmed to room temperature The mixture was then transferred to a syringe added dropwise to a flask containing After the addition the reaction mixture was stirred at room temperature for 18 hours The mixture was cooled in an ice bath quenched with 150 mL of 3M hydrochloric acid The organic layer was separated the aqueous layer was extracted with EtOAc extracted further with CH2Cl2 dried over MgSO4 concentrated The crude oil was purified by chromatography (0-40% EtOAc/hexanes)

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

Procedure: Hydroxylamine hydrochloride (17.1 g, 246 mmol) and sodium acetate (20.2 g, 246 mmol) were added to 110 mL of methanol and the resulting white slurry was stirred at room temperature for 30 min. Propiophenone (30 g, 224 mmol) was added and the mixture was stirred at room temperature for 20 hours. Water (100 mL) was added and the mixture was stirred for 10 min. The product was extracted with EtOAc and the organic layer was washed with saturated NaHCO3 solution and dried over MgSO4. The solvent was evaporated in vacuo to give 32.4 g of the title compound. 1H NMR (CDCl3, 200 MHz): δ=9.21 (s, 1H), 7.60-7.72 (m, 2H), 7.38-7.50 (m, 3H), 2.91 (q, 2H, J=7.8 Hz), 1.23 (t, 3H, J=7.4 Hz). the mixture was stirred at room temperature for 20 hours the mixture was stirred for 10 min The product was extracted with EtOAc the organic layer was washed with saturated NaHCO3 solution dried over MgSO4 The solvent was evaporated in vacuo

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

Procedure: A solution of 5.0 g of propiophenone oxime in 35 ml of dimethylformamide is added dropwise to a solution of 1.55 g of 62.5% sodium hydride in 80 ml of dimethylformamide under ice-colling, and the mixture is stirred at the same temperature for 20 minutes. A solution of 4.24 g of 2-chlorobenzonitrile in 20 ml of dimethylformamide is added dropwise to the mixture and the mixture is stirred at room temperature for 3 hours. The reaction mixture is poured into ice-water and the aqueous mixture is extracted with ethyl acetate. The extract is washed with a saturated sodium chloride solution, dried and evaporated to remove solvent. The residue is purified by silica gel column chromatography (solvent; n-hexane:ethyl acetate=6:1) to give 2.19 g of propiophenone O-(2-cyanophenyl)oxime as oil. the mixture is stirred at room temperature for 3 hours the aqueous mixture is extracted with ethyl acetate The extract is washed with a saturated sodium chloride solution dried evaporated to remove solvent The residue is purified by silica gel column chromatography (solvent; n-hexane:ethyl acetate=6:1)