2,2-Difluoroethan-1-ol → Ethyl 2-(2,2-Difluoroethyl)oxy-5-nitro-benzoate

HRID 1846084Notes

Reaction equation

HRID 1846084 reaction equation
[F:1][CH:2]([F:5])[CH2:3][OH:4].CC([O-])(C)C.[K+].F[C:13]1[CH:23]=[CH:22][C:21]([N+:24]([O-:26])=[O:25])=[CH:20][C:14]=1[C:15]([O:17][CH2:18][CH3:19])=[O:16]>C1COCC1.O>[F:1][CH:2]([F:5])[CH2:3][O:4][C:13]1[CH:23]=[CH:22][C:21]([N+:24]([O-:26])=[O:25])=[CH:20][C:14]=1[C:15]([O:17][CH2:18][CH3:19])=[O:16]

Participants

6

Reactant 3

HCID 1361872,2-Difluoroethan-1-ol2×HCID 12793176Ethyl 2-fluoro-5-nitrobenzoateHCID 23665647Potassium tert-butoxide2×

Product 1

HCID 86658666Ethyl 2-(2,2-Difluoroethyl)oxy-5-nitro-benzoate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

A mixture of 2,2-difluoroethanol (0.178 mL, 2.82 mmol) and KOtBu (0.319 g, 2.70 mmol) in 10 mL THF was stirred for 5 min, then ethyl 2-fluoro-5-nitrobenzoate (0.500 g, 2.35 mmol) was added and it was stirred at rt overnight. Additional 60 μL 2,2-difluoroethanol and 110 mg KOtBu were added and it was stirred for 2 h. The mixture was diluted with H2O, concentrated i.vac. and extracted 2× with EtOAc. The combined organic layers were dried with Na2SO4 and concentrated to furnish the subtitle compound. Yield: 0.52 g (81%); TLC: Rf=0.85 (silica gel, DCM:EtOH 99:1).

Workup

  1. stirringit was stirred at rt overnight
  2. stirringit was stirred for 2 h
  3. concentrationconcentrated i.vac
  4. extractionand extracted 2× with EtOAc
  5. dry with materialThe combined organic layers were dried with Na2SO4
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-2e1c405b9c68412e93efd17a1d270ef4
Source dataset
uspto-grants-2015_02
Patent number
US08951999B2

Reaction notes

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