Methanesulfonyl chloride → HCID 70159695, compound

HRID 2304377Notes

Reaction equation

HRID 2304377 reaction equation
[OH:1][C@@H:2]([CH2:6][C:7]1[CH:12]=[CH:11][C:10]([OH:13])=[C:9]([N+:14]([O-])=O)[CH:8]=1)[C:3]([OH:5])=[O:4].[CH3:17][S:18](Cl)(=[O:20])=[O:19]>CO.[Pd]>[OH:1][C@@H:2]([CH2:6][C:7]1[CH:12]=[CH:11][C:10]([OH:13])=[C:9]([NH:14][S:18]([CH3:17])(=[O:20])=[O:19])[CH:8]=1)[C:3]([OH:5])=[O:4]

Participants

5

Reactant 2

HCID 31297Methanesulfonyl chlorideHCID 59904827HCID 59904827, compound

Product 1

HCID 70159695HCID 70159695, compoundYield 63%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

A solution of (S)-2-hydroxy-3-(4-hydroxy-3-nitrophenyl)propanoic acid (9.2 g, 41 mmol) in 150 mL of methanol was hydrogenated, after addition of 0.5 g of 10% palladium on carbon, for 24 h at 45 psi using a Parr shaker. After filtration through Celite under a blanket of nitrogen gas, the volatiles were removed using a rotary evaporator. The flask was flushed with nitrogen before addition of 30 mL of dry pyridine. Once the stirred suspension formed a homogeneous solution, the flask was cooled-under nitrogen to −20° and methanesulfonyl chloride (5.0 g, 44 mmol) was added over 5 min. After stirring for 1 h at −20°, the flask was placed in a −12° freezer for 24 h. To quench the reaction, 50 mL of water was added and the volatiles were removed using a rotary evaporator with a bath temperature of 50°. A second 50 mL portion of water was added and removed as previously described. The resultant crude red oil was chromatographed on Mitsubishi Chemical Industries CHP-20P resin (75-150 micron) using 15-25% methanol/water to elute the product. After evaporative removal of methanol, the residual solution was lyophilized to yield 6.8 g (63%) of (S)-2-hydroxy-3-(4-hydroxy-3-(methylsulfonyl)aminophenyl)propanoic acid.

Workup

  1. filtrationAfter filtration through Celite under a blanket of nitrogen gas
  2. customthe volatiles were removed
  3. customa rotary evaporator
  4. customThe flask was flushed with nitrogen before addition of 30 mL of dry pyridine
  5. customOnce the stirred suspension formed a homogeneous solution
  6. customwas cooled-under nitrogen to −20°
  7. waitthe flask was placed in a −12° freezer for 24 h
  8. customTo quench
  9. customthe reaction, 50 mL of water
  10. additionwas added
  11. customthe volatiles were removed
  12. customa rotary evaporator with a bath temperature of 50°
  13. additionA second 50 mL portion of water was added
  14. customremoved
  15. customThe resultant crude red oil was chromatographed on Mitsubishi Chemical Industries CHP-20P resin (75-150 micron)
  16. washto elute the product
  17. customAfter evaporative removal of methanol

Sources & evidence

ORD record
ord-0a30782c02de49cc8fc4650f15437170
Source dataset
uspto-grants-2002_08
Patent number
US06436914B1

Reaction notes

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