Trifluoroacetic acid → HCID 57437813, compound

HRID 2114368Notes

Reaction equation

HRID 2114368 reaction equation
[CH3:1][O:2][C:3]1[CH:12]=[CH:11][C:6]2[NH:7][C:8](=[O:10])[O:9][C:5]=2[CH:4]=1.[H-].[Na+].Br[CH2:16][C:17]([O:19][CH2:20][CH3:21])=[O:18].FC(F)(F)C(O)=O>C1COCC1.CC#N.O>[CH3:1][O:2][C:3]1[CH:12]=[CH:11][C:6]2[N:7]([CH2:16][C:17]([O:19][CH2:20][CH3:21])=[O:18])[C:8](=[O:10])[O:9][C:5]=2[CH:4]=1

Participants

7

Reactant 4

HCID 6422Trifluoroacetic acidHCID 7748Ethyl bromoacetateHCID 10772CoixolHCID 24758Sodium hydride

Product 1

HCID 57437813HCID 57437813, compoundYield 81.4%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 18373917Acetonitrile--water (1/1)Solvent

Procedure

A solution of 6-methoxy-2-benzoxazolinone (0.78 g, 4.72 mmol) dissolved in 5 mL of anhydrous THF was added to a suspension of sodium hydride (0.208 g of a 60% dispersion in mineral oil, 5.2 mmol) in 10 mL of anhydrous THF at room temperature and stirred for 10 minutes. Then, ethyl bromoacetate (0.629 mL, 5.67 mmol) was added and stirred at room temperature for two hours. HPLC (Eclipse XDB-C18, 4.6×250 mm, 5 micron, 1-99% CH3CN/H2O with 0.1% trifluoroacetic acid) showed that almost all of the starting material (Rt=4.36 min) was gone and that a new peak (Rt=6.0 min) had formed. The reaction was quenched with 2 mL of 4.0M HCl in dioxane. The solvent was removed by rotary evaporation and the residue was adsorbed onto approximately 10 g of silica gel and purified by column chromatography (40 g silica gel 40 um, gradient elution from 100% dichloromethane to 35% methanol/65% dichloromethane over 40 minutes) to give ethyl [6-(methyloxy)-2-oxo-1,3-benzoxazol-3(2H)-yl]acetate (0.96 g, 3.84 mmol, 81%) as a white crystalline solid. MS (ES) m/e 252 [M+H]+.

Workup

  1. stirringstirred at room temperature for two hours
  2. customhad formed
  3. customThe reaction was quenched with 2 mL of 4.0M HCl in dioxane
  4. customThe solvent was removed by rotary evaporation
  5. custompurified by column chromatography (40 g silica gel 40 um, gradient elution from 100% dichloromethane to 35% methanol/65% dichloromethane over 40 minutes)

Sources & evidence

ORD record
ord-2565488ffcd24cd0a51fb6846a56ba9b
Source dataset
uspto-grants-2008_10
Patent number
US07432258B2

Reaction notes

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