Citric Acid → Citric Acid

HRID 644095Notes

Reaction equation

HRID 644095 reaction equation
[C:1]([OH:13])(=[O:12])[CH2:2][C:3]([CH2:8][C:9]([OH:11])=[O:10])([C:5]([OH:7])=[O:6])[OH:4].[C:14]([O:18][CH2:19][C@H:20]([CH3:47])[O:21][C:22]1[CH:23]=[C:24]([CH:33]=[C:34]([O:36][C:37]2[CH:42]=[CH:41][C:40]([S:43]([CH3:46])(=[O:45])=[O:44])=[CH:39][CH:38]=2)[CH:35]=1)[C:25]([O:27][NH2+]C(C)(C)C)=[O:26])([CH3:17])([CH3:16])[CH3:15].CC(OC)(C)C>O>[C:1]([OH:13])(=[O:12])[CH2:2][C:3]([CH2:8][C:9]([OH:11])=[O:10])([C:5]([OH:7])=[O:6])[OH:4].[C:14]([O:18][CH2:19][C@H:20]([CH3:47])[O:21][C:22]1[CH:23]=[C:24]([CH:33]=[C:34]([O:36][C:37]2[CH:42]=[CH:41][C:40]([S:43]([CH3:46])(=[O:45])=[O:44])=[CH:39][CH:38]=2)[CH:35]=1)[C:25]([OH:27])=[O:26])([CH3:17])([CH3:16])[CH3:15]

Participants

6

Reactant 3

HCID 311Citric Acid2×HCID 15413tert-Butyl methyl etherHCID 86622613({3-[(1S)-2-tert-Butoxy-1-methylethoxy]-5-[4-(methylsulfonyl)phenoxy]benzoyl}oxy)(tert-butyl)ammonium

Product 2

HCID 311Citric AcidHCID 592633093-[(1S)-2-tert-Butoxy-1-methylethoxy]-5-[4-(methylsulfonyl)phenoxy]benzoic acid

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

Aqueous citric acid was prepared by dissolving citric acid (7.35 g, 38.25 mmol) in water (100 mL). The aqueous citric acid solution was added to a reaction vessel containing ({3[(1S)-2-tert-butoxy-1-methylethoxy]-5-[4-(methylsulfonyl)phenoxy]benzoyl}oxy)(tert-butyl)ammonium (10 g at 94.6% w/w, 19.13 mmol) and MTBE (80 mL). The two-phase mixture was stirred for 30 minutes at ambient temperature. The two phases were separated, and the aqueous phase was extracted with MTBE (80 mL). The two organic phases were combined and washed three times with brine (3×80 mL), followed by water (2×80 mL). The combined MTBE extract was distilled down to low volume, fresh MTBE (80 mL) was added and the mixture was distilled down to low volume. Acetonitrile (120 mL) was added and the mixture was distilled down to low volume at 50° C., 209 mbar. This azeodrying was repeated once more to provide a dry acetonitrile solution of the title compound, which was used directly in the next stage.

Workup

  1. customThe two phases were separated
  2. extractionthe aqueous phase was extracted with MTBE (80 mL)
  3. washwashed three times with brine (3×80 mL)
  4. extractionThe combined MTBE extract
  5. distillationwas distilled down to low volume, fresh MTBE (80 mL)
  6. additionwas added
  7. distillationthe mixture was distilled down to low volume
  8. additionAcetonitrile (120 mL) was added
  9. distillationthe mixture was distilled down to low volume at 50° C.

Sources & evidence

ORD record
ord-6f89cc525c564682bf85bd31264dadd7
Source dataset
uspto-grants-2010_04
Patent number
US07700640B2

Reaction notes

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