Formic Acid → 1-(4-Fluorophenyl)-2-nitroethanol

HRID 2120008Notes

Reaction equation

HRID 2120008 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:13])[CH2:9][N+:10]([O-:12])=[O:11])=[CH:4][CH:3]=1.C(N(CC)CC)C.C(O)=O.CN(C)C=O>CC1C=CC(C(C)C)=CC=1.CC1C=CC(S([N-][C@H]([C@@H](N)C2C=CC=CC=2)C2C=CC=CC=2)(=O)=O)=CC=1.[Cl-].[Ru+2].O>[F:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]([OH:13])[CH2:9][N+:10]([O-:12])=[O:11])=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 284Formic AcidHCID 6228DimethylformamideHCID 8471TriethylamineHCID 112868511-(4-Fluorophenyl)-2-nitroethanone

Product 1

HCID 112983621-(4-Fluorophenyl)-2-nitroethanolYield 80%

Reagents, catalysts & solvents 2

HCID 11549108RuCl[(S,S)-Tsdpen](p-cymene)CatalystHCID 962WaterSolvent

Procedure

A 50 ml Schlenk flask was charged with 1.831 g (10.0 mmol) of 1-(4-fluorophenyl)-2-nitroethanone, 3.35 ml (24.0 mmol) of triethylamine, 2.26 ml (60.0 mmol) of formic acid, 10 ml of dimethylformamide (DMF), and 31.8 mg (0.05 mmol, S/C=200) of RuCl[(S,S)-Tsdpen](p-cymene) under an atmosphere of argon, and stirring was carried out at 30° C. for 16 hours. The reaction solution was poured into water and extracted with ether, and the organic layer was washed with saturated brine and then dried with anhydrous sodium sulfate. After removing the drying agent, the solvent was distilled off, and the oil so obtained was purified by silica gel column chromatography (eluant; n-hexane:ethyl acetate=9:1) to give 1.48 g of optically active 1-(4-fluorophenyl)-2-nitroethanol. 1H-NMR supported it was the target product, and the yield was 80%.

Workup

  1. extractionextracted with ether
  2. washthe organic layer was washed with saturated brine
  3. dry with materialdried with anhydrous sodium sulfate
  4. customAfter removing the drying agent
  5. distillationthe solvent was distilled off
  6. customthe oil so obtained
  7. customwas purified by silica gel column chromatography (eluant; n-hexane:ethyl acetate=9:1)

Sources & evidence

ORD record
ord-472b8aec64004447963c91e5831c19eb
Source dataset
uspto-grants-2004_02
Patent number
US06686505B2

Reaction notes

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