3,5-Dinitrobenzoic acid → [(1S)-1-[(2R)-2-(2-fluorophenyl)-2-oxiranyl)ethyl] 3,5-dinitrobenzoate

HRID 482057Notes

Reaction equation

HRID 482057 reaction equation
FC1C=CC=CC=1C1([C@H](OC2CCCCO2)C)CO1.[F:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][C:22]=1[C:27]1([C@H:30]([OH:32])[CH3:31])[CH2:29][O:28]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[N+:52]([C:55]1[CH:56]=[C:57]([CH:61]=[C:62]([N+:64]([O-:66])=[O:65])[CH:63]=1)[C:58](O)=[O:59])([O-:54])=[O:53].N(C(OCC)=O)=NC(OCC)=O.C(OC(C)C)(C)C>O1CCCC1.O.C(OCC)(=O)C>[N+:52]([C:55]1[CH:56]=[C:57]([CH:61]=[C:62]([N+:64]([O-:66])=[O:65])[CH:63]=1)[C:58]([O:32][C@H:30]([C@@:27]1([C:22]2[CH:23]=[CH:24][CH:25]=[CH:26][C:21]=2[F:20])[CH2:29][O:28]1)[CH3:31])=[O:59])([O-:54])=[O:53]

Participants

10

Reactant 6

HCID 74333,5-Dinitrobenzoic acidHCID 7914Diisopropyl EtherHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 538608792-(2-fluorophenyl)-2-[(1R)-1-(3,4,5,6-tetrahydro-2H-pyran-2-yl)oxyethyl]oxiraneHCID 86749723(1R)-1-[2-(2-fluorophenyl)-2-oxiranyl]ethanol

Product 1

HCID 86749722[(1S)-1-[(2R)-2-(2-fluorophenyl)-2-oxiranyl)ethyl] 3,5-dinitrobenzoate

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

In the same manner as in Reference Example 1, starting from 2-(2-fluorophenyl)-2-[(1R)-1-(3,4,5,6-tetrahydro-2H-pyran-2-yl)oxyethyl]oxirane (synthesized by the method described in EP 0548553A), (1R)-1-[2-(2-fluorophenyl)-2-oxiranyl] ethanol was obtained. To a solution of this product (34.77 g) in tetrahydrofuran (600 ml) were added, with ice cooling, 127.21 g of triphenyl phosphine, 102.88 g of 3,5-dinitrobenzoic acid and 84.47g of diethyl azodicarboxylate, and the resulting mixture was stirred at room temperature for 7 hours under an atmosphere of argon. To the reaction solution were added 600 ml of ethyl acetate, 100 ml of diisopropyl ether and 800 ml of water to fractionate and the aqueous layer was extracted with ethyl acetate (600 ml, 400 ml). The organic layers were combined, washed with water and a saturated aqueous solution of sodium chloride successively, then dried over anhydrous magnesium sulfate and concentrated. The residue was purified by silica gel column chromatography (eluent: hexane/ethyl acetate=5/1) to give 23.15 g of [(1S)-1-[(2R)-2-(2-fluorophenyl)-2-oxiranyl)ethyl] 3,5-dinitrobenzoate as colorless needles.

Workup

  1. customsynthesized by the method
  2. customwas obtained
  3. extractionthe aqueous layer was extracted with ethyl acetate (600 ml, 400 ml)
  4. washwashed with water
  5. dry with materiala saturated aqueous solution of sodium chloride successively, then dried over anhydrous magnesium sulfate
  6. concentrationconcentrated
  7. customThe residue was purified by silica gel column chromatography (eluent: hexane/ethyl acetate=5/1)

Sources & evidence

ORD record
ord-d5f90598d1b243b4a89eff3ec918f657
Source dataset
uspto-grants-1998_08
Patent number
US05792780

Reaction notes

Loading…