5-Fluoro-2-nitrophenol → 4-(5-fluoro-2-nitrophenoxy)tetrahydro-2H-pyran

HRID 450531Notes

Reaction equation

HRID 450531 reaction equation
N(C(OC(C)(C)C)=O)=NC(OC(C)(C)C)=O.[F:17][C:18]1[CH:19]=[CH:20][C:21]([N+:25]([O-:27])=[O:26])=[C:22]([OH:24])[CH:23]=1.[O:28]1[CH2:33][CH2:32][CH:31](O)[CH2:30][CH2:29]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(Cl)Cl>[F:17][C:18]1[CH:19]=[CH:20][C:21]([N+:25]([O-:27])=[O:26])=[C:22]([CH:23]=1)[O:24][CH:31]1[CH2:32][CH2:33][O:28][CH2:29][CH2:30]1

Participants

6

Reactant 4

HCID 99375-Fluoro-2-nitrophenolHCID 11776TriphenylphosphineHCID 74956Tetrahydro-4H-pyran-4-olHCID 97268Di-tert-butyl azodicarboxylate

Product 1

HCID 533521804-(5-fluoro-2-nitrophenoxy)tetrahydro-2H-pyran

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Di-tert-butyl azodicarboxylate (17.6 g, 76.4 mmol) was added into a solution of 5-fluoro-2-nitrophenol (10 g, 63.7 mmol), tetrahydro-2H-pyran-4-ol (7.3 mL, 76.4 mmol) and triphenyl phosphine (20 g, 76.4 mmol) in anhydrous DCM (120 mL) at 0° C. The solution was allowed to warm to ambient temperature overnight, concentrated in vacuo and the crude product triturated with n-pentane/diethyl ether (×2) to remove the triphenyl phosphine oxide (16.5 g) by-product. The sample was purified by flash column chromatography (5:1 petroleum ether (40-60° C.)/EtOAc) to yield yellow oil which was used in the next step directly.

Workup

  1. concentrationconcentrated in vacuo
  2. customthe crude product triturated with n-pentane/diethyl ether (×2)
  3. customto remove the triphenyl phosphine oxide (16.5 g) by-product
  4. customThe sample was purified by flash column chromatography (5:1 petroleum ether (40-60° C.)/EtOAc)
  5. customto yield yellow oil which

Sources & evidence

ORD record
ord-de97990ce20247a6867775d502d50954
Source dataset
uspto-grants-2013_07
Patent number
US08486953B2

Reaction notes

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