反应详情

温度

50 °C

To an ice cold (0-5° C.) dimethylformamide (6.2 mL, 80 mmol) was added phosphorous oxychloride (3.75 mL, 40 mmol) dropwise with stirring for 15 min. To this cold mixture, tert-butyl methyl ketone (2.0 g, 20 mmol) was added dropwise maintaining the temperature of the reaction mixture between 45-55° C. for 10 min. The reaction mixture was slowly allowed to room temperature (rt) and stand for 30 min. To the reaction mixture, 1 mL of a total solution of hydroxylamine hydrochloride (5.56 g, 80 mmol) in dry DMF (8 mL) was added and the mixture was stirred at 70-80° C. for 5 min. Then the remaining solution of hydroxylamine hydrochloride in DMF was added thereafter at such a rate that the temperature of the reaction mixture rise above 145-155° C. After completion of the addition, the reaction mixture was allowed to rt for 30 min and diluted with cold water (200 mL). The solution was extracted with chloroform (3×100 mL) and the combined chloroform layer was washed with water, brine and dried over sodium sulfate. The solution was filtered and evaporated the solvent. The residue was chromatographed over silica gel using hexane-ethyl acetate (98:2) as eluent to give the product as a light green color oil (1.0 g, 35%). 1H NMR (400 MHz, CDCl3): δ 5.56 (1H, s, ═CH), 1.24 (9H, s, tert-butyl).

1. customwas slowly allowed to room temperature
2. custom(rt)
3. waitstand for 30 min
4. stirringthe mixture was stirred at 70-80° C. for 5 min
5. customrise above 145-155° C
6. additionAfter completion of the addition
7. waitthe reaction mixture was allowed to rt for 30 min
8. extractionThe solution was extracted with chloroform (3×100 mL)
9. washthe combined chloroform layer was washed with water, brine
10. dry with materialdried over sodium sulfate
11. filtrationThe solution was filtered
12. customevaporated the solvent
13. customThe residue was chromatographed over silica gel