Ethyl trifluoroacetate → HCID 12040691, compound

HRID 1369171Notes

Reaction equation

HRID 1369171 reaction equation
[CH2:1]([O:3][C:4]1[CH:15]=[CH:14][C:7]([CH2:8][C@@H:9]([C:11]([OH:13])=[O:12])[NH2:10])=[CH:6][CH:5]=1)[CH3:2].CN(C)C(=N)N(C)C.[F:24][C:25]([F:32])([F:31])[C:26](OCC)=[O:27]>CO>[CH2:1]([O:3][C:4]1[CH:15]=[CH:14][C:7]([CH2:8][C@@H:9]([C:11]([OH:13])=[O:12])[NH:10][C:26](=[O:27])[C:25]([F:32])([F:31])[F:24])=[CH:6][CH:5]=1)[CH3:2]

Participants

5

Reactant 3

HCID 9794Ethyl trifluoroacetateHCID 664601,1,3,3-TetramethylguanidineHCID 11275812O-Ethyl-L-tyrosine

Product 1

HCID 12040691HCID 12040691, compound

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

O-Ethyl-L-tyrosine (IV, EXAMPLE 3, 20.9 g, 100 mmol) is suspended in methanol (100 mL), tetramethylguanidine (TMG) (12.5 mL, 100 mmol) is added, followed by ethyl trifluoroacetate (14 mL, 120 mmol). The mixture is stirred at 20-25 deg for 48 hr and the resulting mixture is concentrated to remove most of the methanol and excess ethyl trifluoroacetate. The residue is dissolved in water (40 mL), added hydrochloric acid (100 mL of 1.0 M) to adjust the pH<3. The mixture is stirred at 20-25° for at least 2 hr, then filtered. The precipitate is suspended in water (50 mL), stirred for 0.5 hr, then filtered. This wash process is repeated once. Then the precipitate is dried in oven at 55° for 48 hr to give the title compound, NMR (DMSO-d6) δ12.9, 9.72, 7.15, 6.82, 4.46, 3.98, 3.15, 2.92 and 1.31; CMR (DMSO-d6) δ171.8, 157.6, 157.7, 130.3, 129.0, 116.1, 63.2, 54.6, 35.1 and 15.0; FMR (DMSO-d6) δ-74.7; HRMS (FAB) calculated for C13H14F3NO4 [M+1]=306.0953, found=306.0952.

Workup

  1. concentrationthe resulting mixture is concentrated
  2. customto remove most of the methanol and excess ethyl trifluoroacetate
  3. dissolutionThe residue is dissolved in water (40 mL)
  4. additionadded hydrochloric acid (100 mL of 1.0 M)
  5. stirringThe mixture is stirred at 20-25° for at least 2 hr
  6. filtrationfiltered
  7. stirringstirred for 0.5 hr
  8. filtrationfiltered
  9. customThen the precipitate is dried in oven at 55° for 48 hr

Sources & evidence

ORD record
ord-4909426c9e384d3bbc13668432961e2d
Source dataset
uspto-grants-2003_06
Patent number
US06576769B2

Reaction notes

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