Acetic Acid → HCID 10694967, compound

HRID 1489415Notes

Reaction equation

HRID 1489415 reaction equation
[F:1][C:2]([F:20])([CH:17]([F:19])[F:18])[CH2:3][O:4][C:5]1[CH:10]=[CH:9][C:8]([N:11]2[CH:15]=[N:14][NH:13][C:12]2=[O:16])=[CH:7][CH:6]=1.FC(F)(F)S(O[C@@H:27]([CH3:38])[C:28]([O:30][CH2:31][C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1)=[O:29])(=O)=O.C(O)(=O)C>CN(C)C=O.[H-].[Na+].O1CCCC1.C(OCC)(=O)C.C(OC(C)C)(C)C>[F:20][C:2]([F:1])([CH:17]([F:19])[F:18])[CH2:3][O:4][C:5]1[CH:10]=[CH:9][C:8]([N:11]2[C:12](=[O:16])[N:13]([C@H:27]([CH3:38])[C:28]([O:30][CH2:31][C:32]3[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=3)=[O:29])[N:14]=[CH:15]2)=[CH:7][CH:6]=1

Participants

9

Reactant 3

HCID 176Acetic AcidHCID 10779907HCID 10779907, compoundHCID 10881508Phenylmethyl (2S)-2-[[(trifluoromethyl)sulfonyl]oxy]propanoate

Product 1

HCID 10694967HCID 10694967, compoundYield 85.6%

Reagents, catalysts & solvents 5

HCID 6228DimethylformamideSolventHCID 7914Diisopropyl EtherSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolventHCID 24758Sodium hydrideSolvent

Procedure

4-[4-(2,2,3,3-Tetrafluoropropoxy)phenyl]-3(2H,4H)-1,2,4-triazolone (18 g) was dissolved in 180 ml of dimethylformamide, to which 60% sodium hydride in oil (2.52 g) was added. The mixture was vigorously stirred at room temperature for 40 minutes. The reaction solution was added to a solution of 20 g of benzyl (2S)-2-trifluoromethanesulfonyloxypropionate prepared in Example 3 in 240 ml of tetrahydrofuran under nitrogen atmosphere at -40° to -30° C. over the period of ca. 40 minutes. The mixture was stirred at -40° to -20° C. for 40 minutes, to which 10 ml of acetic acid was added. Then, the reaction solution was diluted with a mixture of 100 ml of ethyl acetate and 500 ml of diisopropyl ether, washed with 250 ml of water, 2N-hydrochloric acid (250 ml×2) and 250 ml of an aqueous solution of sodium chloride successively. After dring over magnesium sulfate, the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography (silica gel: 250 g, eluent; hexane:ethyl acetate=2:1) to give 24 g of benzyl (2R)-2-[4-[4-(2,2,3,3-tetrafluoropropoxy)phenyl]-4,5-dihydro-5-oxo-1H-1,2,4-triazol-1-yl]propionate (yield: 82%) as a colorless oil.

Workup

  1. additionwas added
  2. additionwas added
  3. washwashed with 250 ml of water, 2N-hydrochloric acid (250 ml×2) and 250 ml of an aqueous solution of sodium chloride successively
  4. distillationthe solvent was distilled off under reduced pressure
  5. customThe residue was purified by silica gel chromatography (silica gel: 250 g, eluent; hexane:ethyl acetate=2:1)

Sources & evidence

ORD record
ord-0e9491efff11447b8873c584ef7f8c42
Source dataset
uspto-grants-1997_10
Patent number
US05677464

Reaction notes

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