Реакция #62971

Уравнение реакции

sodium bisulfite

hydrochloric acid

sodium bisulfite

hydrochloric acid

sodium chloride

sodium hydroxide

6,6-dibromopenicillanic acid

→

6,6-dibromopenicillanic acid 1,1-dioxide

Растворители

water

ethyl acetate

dichloromethane

Условия реакции

Обработка

1. 1
   ДругоеThe aqueous layer was removed
2. 2
   Экстракцияthe organic layer was extracted with water (2×100 ml)
3. 3
   workup.ADDITIONTo the combined aqueous solutions was added, at -5° C.
4. 4
   Другоеa premixed solution prepared from 59.25 g of potassium permanganate, 18 ml of concentrated phosphoric acid and 600 ml of water, until the pink color of the permanganate
5. 5
   workup.ADDITIONThe addition
6. 6
   Другоеthe two phases were separated
7. 7
   ЭкстракцияThe aqueous solution was extracted with additional ethyl acetate (2×150 ml)
8. 8
   Промывкаthe combined ethyl acetate solutions were washed with brine
9. 9
   Сушкаdried (MgSO4)

Методика

To the dichloromethane solution of 6,6-dibromopenicillanic acid from Preparation A was added 300 ml of water, followed by the dropwise addition over a period of 30 minutes of 105 ml of 3N sodium hydroxide. The pH stabilized at 7.0. The aqueous layer was removed and the organic layer was extracted with water (2×100 ml). To the combined aqueous solutions was added, at -5° C., a premixed solution prepared from 59.25 g of potassium permanganate, 18 ml of concentrated phosphoric acid and 600 ml of water, until the pink color of the permanganate persisted. The addition took 50 minutes and 550 ml of oxidant were required. At this point 500 ml of ethyl acetate was added and then the pH was lowered to 1.23 by the addition of 105 ml of 6N hydrochloric acid. Then 250 ml of 1M sodium bisulfite was added during 10-15 minutes at ca. 10° C. During the addition of the sodium bisulfite solution the pH was maintained at 1.25 -1.35 using 6N hydrochloric acid. The aqueous phase was saturated with sodium chloride and the two phases were separated. The aqueous solution was extracted with additional ethyl acetate (2×150 ml) and the combined ethyl acetate solutions were washed with brine and dried (MgSO4). This afforded an ethyl acetate solution of 6,6-dibromopenicillanic acid 1,1-dioxide

Источник