Water → (S)-2-((4-Nitrophenoxy)methyl)oxirane

HRID 2223424Notes

Reaction equation

HRID 2223424 reaction equation
[CH:1]1[C:6]([N+:7]([O-:9])=[O:8])=[CH:5][CH:4]=[C:3]([OH:10])[CH:2]=1.[F-].[Cs+].S(C1C=CC([N+]([O-])=O)=CC=1)(O[CH2:17][C@H:18]1[O:20][CH2:19]1)(=O)=O.O>CN(C=O)C>[N+:7]([C:6]1[CH:5]=[CH:4][C:3]([O:10][CH2:17][C@H:18]2[O:20][CH2:19]2)=[CH:2][CH:1]=1)([O-:9])=[O:8]

Participants

6

Reactant 4

HCID 962WaterHCID 9804-NitrophenolHCID 25953Cesium fluorideHCID 10868995(S)-(+)-Glycidyl-4-nitrobenzoate

Product 1

HCID 147859(S)-2-((4-Nitrophenoxy)methyl)oxiraneYield 93.9%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

p-Nitrophenol (0.92 g, 6.6 mmol) was dissolved in 5 ml anhydrous DMF and cesium fluoride (3.02 g, 19.9 mmol) was added. The reaction mixture was stirred for 1 hour at room temperature and (S)-Glycidyl nosylate (1.71 g, 6.6 mmol) was added. The system was stirred for an additional 24 hours at room temperature. Water (150 ml) was added, and the solution was extracted with ethylacetate. The organic phase was dried over MgSO4 and evaporated. The residue was purified with column chromatograph using ethylacetate:hexane (50:50) solvent system to give (S)-Glycidyl p-nitrophenyl ether (99.6% ee, based on chiral HPLC with Chiralcel OD, m.p 78-9° C.) as a yellowish solid (1.21 g, 93% yield). The NMR values are the same as the literature values for the racemic mixture: 1H-NMR (CDCl3) δ 2.78 (dd, 1H), 2.95 (t 1H), 3.39 (m 1H), 4.0 (dd, 1H), 4.38 (dd, 1H), 6.99 (dd, 2H), 8.2 (dd, 2H).

Workup

  1. stirringThe system was stirred for an additional 24 hours at room temperature
  2. extractionthe solution was extracted with ethylacetate
  3. dry with materialThe organic phase was dried over MgSO4
  4. customevaporated
  5. customThe residue was purified with column chromatograph

Sources & evidence

ORD record
ord-74bb51c0a1e749919d11399a06acb9d5
Source dataset
uspto-grants-2008_05
Patent number
US07375136B2

Reaction notes

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