Acetyl chloride → N-formyl-Tyr(3-tBu)-OMe

HRID 1988290Notes

Reaction equation

HRID 1988290 reaction equation
[C:1](Cl)(=[O:3])C.C([O-])=O.[Na+].[NH2:9][C@H:10]([C:23]([O:25][CH3:26])=[O:24])[CH2:11][C:12]1[CH:17]=[CH:16][C:15]([OH:18])=[C:14]([C:19]([CH3:22])([CH3:21])[CH3:20])[CH:13]=1.C([O-])(O)=O.[Na+]>C(OCC)C.C(Cl)Cl>[NH:9]([CH:1]=[O:3])[C@H:10]([C:23]([O:25][CH3:26])=[O:24])[CH2:11][C:12]1[CH:17]=[CH:16][C:15]([OH:18])=[C:14]([C:19]([CH3:22])([CH3:20])[CH3:21])[CH:13]=1

Participants

7

Reactant 4

HCID 6367Acetyl chlorideHCID 516892Sodium BicarbonateHCID 2723810Sodium FormateHCID 15549498Tyr(3-tBu)-OMe

Product 1

HCID 131727520N-formyl-Tyr(3-tBu)-OMeYield 101.7%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of acetyl chloride (22.6 ml, 299 mmol) in diethyl ether (11), sodium formate (30.6 g, 450 mmol) was added under cooling with ice and stirred at room temperature for 23 hours. The reaction mixture was filtered and evaporated to remove the solvent. The thus obtained residue was added dropwise to a solution of H-Tyr(3-tBu)-OMe (22.2 g, 83.8 mmol) in methylene chloride (500 ml) under cooling with ice, mixed with TEA (46.7 ml, 335 mmol) and stirred at room temperature for 2 hours. The reaction mixture was mixed with saturated aqueous NaHCO3 and extracted with chloroform. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and evaporated to remove the solvent under reduced pressure. The thus obtained residue was subjected to silica gel column chromatography (developing solvent: n-hexane:ethyl acetate=1:1), giving N-formyl-Tyr(3-tBu)-OMe (23.8 g, 100%).

Workup

  1. temperatureunder cooling with ice
  2. filtrationThe reaction mixture was filtered
  3. customevaporated
  4. customto remove the solvent
  5. temperatureunder cooling with ice
  6. stirringstirred at room temperature for 2 hours
  7. extractionextracted with chloroform
  8. washThe organic layer was washed with saturated brine
  9. dry with materialdried over anhydrous magnesium sulfate
  10. customevaporated
  11. customto remove the solvent under reduced pressure

Sources & evidence

ORD record
ord-c9b4db90f79e47399ecc926c81cc576b
Source dataset
uspto-grants-2009_06
Patent number
US07553969B1

Reaction notes

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