Hydrochloric Acid → 6,6-Dibromopenicillanic acid sulfone

HRID 986679

Reaction equation

HRID 986679 reaction equation
[CH3:1][C:2]1([CH3:15])S[C@@H:5]2[C:7]([Br:11])([Br:10])[C:8](=[O:9])[N:4]2[C@H:3]1[C:12]([OH:14])=[O:13].[OH-].[Na+].Cl.[S:19](=[O:22])(O)[O-:20].[Na+].[Cl-].[Na+]>C(OCC)(=O)C.O.ClCCl>[CH3:1][C:2]1([CH3:15])[S:19](=[O:22])(=[O:20])[C@@H:5]2[C:7]([Br:10])([Br:11])[C:8](=[O:9])[N:4]2[C@H:3]1[C:12]([OH:14])=[O:13]

Participants

9

Reactant 5

HCID 313Hydrochloric Acid2×HCID 5234Sodium ChlorideHCID 14798Sodium HydroxideHCID 903766,6-Dibromopenicillanic acidHCID 23665763Sodium Bisulfite2×

Product 1

HCID 14277206,6-Dibromopenicillanic acid sulfone

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

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.

Workup

  1. customThe aqueous layer was removed
  2. extractionthe organic layer was extracted with water (2×100 ml)
  3. additionTo the combined aqueous solutions was added, at -5° C.
  4. customa 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. additionThe addition
  6. customthe two phases were separated
  7. extractionThe aqueous solution was extracted with additional ethyl acetate (2×150 ml)
  8. washthe combined ethyl acetate solutions were washed with brine
  9. dry with materialdried (MgSO4)

Sources & evidence

ORD record
ord-96931031178a448489844201a4c227fc
Source dataset
uspto-grants-1987_12
Patent number
US04714761

Linked notes

Loading…