Formic Acid → For-Orn(Z)-OH

HRID 9708

Reaction equation

HRID 9708 reaction equation
[NH2:1][C@H:2]([C:17]([OH:19])=[O:18])[CH2:3][CH2:4][CH2:5][NH:6][C:7]([O:9][CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)=[O:8].[CH:20](O)=[O:21].C(OC(=O)C)(=O)C>O>[NH:1]([CH:20]=[O:21])[C@H:2]([C:17]([OH:19])=[O:18])[CH2:3][CH2:4][CH2:5][NH:6][C:7]([O:9][CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)=[O:8]

Participants

5

Reactant 3

HCID 284Formic AcidHCID 7918Acetic AnhydrideHCID 7009570H-Orn(Z)-OH

Product 1

HCID 11666482For-Orn(Z)-OHYield 88%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

444.7 g (1.67 mole) of commercially available H-Orn(Z)-OH was dissolved in 3.5 L (93 moles) of formic acid. The solution was cooled in an ice bath, and 1.17 L (12 moles) of acetic anhydride was subsequently added in dropwise fashion over two hours while the temperature of the reaction mixture was maintained between about 5° and 15° C. The resultant reaction mixture was stirred at room temperature for about two hours after the addition was completed, and the reaction vessel was refrigerated overnight. 1.5 L of cold water was then added, and the solution was concentrated to dryness under reduced pressure. The residual, light yellow syrup was taken up into EtOAc, washed with water and then with saturated NaCl, and then dried overnight over sodium sulfate. After filtration and evaporation to dryness, the residual syrup was dissolved in 5 L of ethyl ether. The solution was cooled in a dry ice bath and seeded. The resulting crystalline product was filtered, washed with ethyl ether, air dried for two hours and finally dried in a lyophilizer. 431.6 g (1.47 mole, 88%) of For-Orn(Z)-OH was obtained.

Workup

  1. temperatureThe solution was cooled in an ice bath
  2. temperaturewas maintained between about 5° and 15° C
  3. customThe resultant reaction mixture
  4. additionafter the addition
  5. waitthe reaction vessel was refrigerated overnight
  6. concentrationthe solution was concentrated to dryness under reduced pressure
  7. washwashed with water
  8. dry with materialwith saturated NaCl, and then dried overnight over sodium sulfate
  9. filtrationAfter filtration and evaporation to dryness
  10. dissolutionthe residual syrup was dissolved in 5 L of ethyl ether
  11. temperatureThe solution was cooled in a dry ice bath
  12. filtrationThe resulting crystalline product was filtered
  13. washwashed with ethyl ether, air
  14. customdried for two hours
  15. customfinally dried in a lyophilizer

Sources & evidence

ORD record
ord-9b97e0b01ff54db5b0b5a0234ecca14d
Source dataset
uspto-grants-2006_08
Patent number
US07091314B2

Linked notes

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