反应详情

To a solution of diethyl 3-(N-hydroxyamino)propylphosphonate (2.80 g.) in chloroform (30 ml.) was added dropwise a mixture of acetic anhydride (2.04 g.) and formic acid (1.38 g.), which was prepared in the same manner as that of Example (31), under ice-cooling with stirring. The reaction mixture was stirred for half an hour at 0°-5° C. and for additional an hour at ambient temperature, and then evaporated to dryness under reduced pressure to give an oily residue, which was dissolved in a mixture of methanol (15 ml.) and water (5 ml.), adjusted to pH 8 with 1N aqueous sodium hydroxide solution and stirred for 1.5 hours at ambient temperature. The methanol was distilled off from this solution under reduced pressure to give an aqueous solution, which was adjusted to pH 5 with 10% hydrochloric acid and extracted with chloroform (once with 30 ml. portion and three times with 10 ml. portions). These combined extracts were dried over magnesium sulfate and evaporated to dryness under reduced pressure to give crude diethyl 3-(N-formyl-N-hydroxyamino)propylphosphonate (2.89 g.), which was passed through a column packed with silica gel (60 g.). The column was eluted with a mixture of chloroform and methanol (25:1 by volume), and the fractions containing an object compound were collected and evaporated to dryness under reduced pressure to give the same pure object compound (1.71 g.).

1. customwas prepared in the same manner as that of Example (31)
2. temperatureunder ice-cooling
3. stirringThe reaction mixture was stirred for half an hour at 0°-5° C. and for additional an hour at ambient temperature
4. customevaporated to dryness under reduced pressure
5. customto give an oily residue, which
6. stirringstirred for 1.5 hours at ambient temperature
7. distillationThe methanol was distilled off from this solution under reduced pressure
8. customto give an aqueous solution, which
9. extractionextracted with chloroform (once with 30 ml
10. dry with materialThese combined extracts were dried over magnesium sulfate
11. customevaporated to dryness under reduced pressure