(NZ)-N-(cyclohexylmethylidene)hydroxylamine

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 solution of the oxime formed in Example 1 (1 g, 8.25 mmol) in HCl (0.5 M in dioxane; 18.16 ml, 9.08 mmol) and DMF (40 ml) was added oxone (2.79 g, 4.54 mmol) and the resulting mixture was stirred overnight at room temperature. The reaction was partitioned between diethylether and water and the layers were separated. The organic layer was washed with saturated ammonium chloride, dried over sodium sulfate, then concentrates in vacuo using a room temperature water bath. The resulting low boiling liquid was carried on directly to the next step. 1H NMR (CDCl3) δ 1.0-2.2 (m, 10H), 2.35 (m, 1H), 7.8 (bd, 1H). The reaction was partitioned between diethylether and water the layers were separated The organic layer was washed with saturated ammonium chloride dried over sodium sulfate using a room temperature

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

実験手順: To a solution of cyclohexanecarbaldehyde (4 ml, 33.02 mmol) in CH2Cl2 (100 ml) at room temperature was added hydroxylamine hydrochloride (2.76 g, 39.62 mmol) followed by Et3N (5.52 ml, 39.62 mmol) and the reaction was stirred overnight. The resulting mixture was partitioned between CH2Cl2 and H2O and the layers were separated. The organic layer was dried over Na2SO4, concentrated in vacuo and used directly for the next step. 1H NMR (CDCl3) δ 1.0-2.0 (m, 10H), 3.0 (m, 1H), 6.6 (d, 0.5H), 7.4 (d, 0.5H), 8.2 (bs, 1H). The resulting mixture was partitioned between CH2Cl2 and H2O the layers were separated The organic layer was dried over Na2SO4 concentrated in vacuo

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

実験手順: A solution of cyclohexanecarboxaldehyde (11.2 g, 100 mmol), hydroxylamine hydrochloride (7.2 g, 104 mmol) and pyridine (8.5 mL) in ethanol (150 mL) was stirred for 18 hours, then concentrated in vacuo. The residue was taken up in 10% aqueous citric acid and extracted with ethyl acetate (3×150 mL). The organics were combined, dried over MgSO4 and concentrated to afford cyclohexanecarboxaldehyde oxime which was used directly in the next step. concentrated in vacuo extracted with ethyl acetate (3×150 mL) dried over MgSO4 concentrated

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

実験手順: To a solution of cyclohexane carboxaldehyde oxime (35.6 g, 280 mmol) in DMF (300 ml) is added N-chlorosuccinimide (39.2 g, 294 mmol) portionwise, while maintaining the reaction temperature below 45° C. On complete addition, the mixture is stirred overnight at room temperature before adding a saturated aqueous NH4Cl solution (900 ml). The mixture is extracted with ethyl acetate. The organic layer is washed successively with water (500 ml) and brine (500 ml), dried (MgSO4), filtered and concentrated. The residue and 5-methyltetrazole (24.7 g, 294 mmol) are diluted in dichloromethane (400 ml) and triethyamine (50.8 ml, 364 mmol) is added dropwise at room temperature. After stirring overnight, the mixture in concentrated and the residue is taken up in ethyl acetate. The solution is washed successively with a saturated aqueous NH4Cl solution, water and brine, then dried (MgSO4), filtered and concentrated. Silica-gel chromatography of the residue affords 16.6 g of 5-methyl-1-(cyclohexylcarbohydroximoyl)-tetrazole [yield 28.3%; 1H-NMR (CDCl3) δppm: 1.1-1.5 (m, 4H), 1.62-1.98 (m, 6H), 2.55 (s, 3H), 2.8 (m, 1H), 9.3 (broad, 1H); HPLC/MS: m/z=210 (M+H)]. while maintaining the reaction temperature below 45° C On complete addition The mixture is extracted with ethyl acetate The organic layer is washed successively with water (500 ml) and brine (500 ml) dried (MgSO4) filtered concentrated After stirring overnight the mixture in concentrated The solution is washed successively with a saturated aqueous NH4Cl solution, water and brine dried (MgSO4) filtered concentrated