Phenol → 1-Bromo-2-nitro-4-phenoxymethyl-benzene

HRID 2197983Notes

Reaction equation

HRID 2197983 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][OH:9])=[CH:4][C:3]=1[N+:10]([O-:12])=[O:11].[C:13]1(O)[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][O:9][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)=[CH:4][C:3]=1[N+:10]([O-:12])=[O:11]

Participants

6

Reactant 4

HCID 996PhenolHCID 11776TriphenylphosphineHCID 5363146Diisopropyl azodicarboxylateHCID 24809228(4-Bromo-3-nitrophenyl)methanol

Product 1

HCID 684618561-Bromo-2-nitro-4-phenoxymethyl-benzeneYield 25%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

The product from Example 221a (0.5 g, 2.15 mmol) was combined with phenol (0.203 g, 2.15 mmol) and triphenylphosphine (0.735 g, 2.80 mmol) in anhydrous THF (7 mL) under nitrogen and the resulting solution cooled in an ice bath. To the cold solution was added dropwise diisopropylazodicarboxylate (0.467 mL, 2.37 mmol). Stirring at 0° C. was continued for 15 min then the cold bath was removed and the reaction mixture allowed to warm to room temperature and 90 min before quench and workup by pouring into dilute HCl and extraction with ether. The combined extracts were dried MgSO4, filtered and concentrated under vacuum giving the crude title compound that was purified by flash chromatography on silica gel eluting with EtOAc-hexanes to give the title compound (0.162 g, 25%).

Workup

  1. temperaturethe resulting solution cooled in an ice bath
  2. customthe cold bath was removed
  3. temperatureto warm to room temperature and 90 min
  4. custombefore quench
  5. additionworkup by pouring into dilute HCl and extraction with ether
  6. filtrationfiltered
  7. concentrationconcentrated under vacuum
  8. customgiving the crude title compound that
  9. customwas purified by flash chromatography on silica gel eluting with EtOAc-hexanes

Sources & evidence

ORD record
ord-fd772206f36342e7b25d95fe335173d4
Source dataset
uspto-grants-2012_12
Patent number
US08338605B2

Reaction notes

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