Triphenylphosphine → 2-Bromo-1-(3-fluorobenzyloxy)-4-nitrobenzene

HRID 458087

Reaction equation

HRID 458087 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[OH:11].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[F:31][C:32]1[CH:33]=[C:34]([CH:37]=[CH:38][CH:39]=1)[CH2:35]O.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1.O.CCOC(C)=O>[Br:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[O:11][CH2:35][C:34]1[CH:37]=[CH:38][CH:39]=[C:32]([F:31])[CH:33]=1

Participants

8

Reactant 4

HCID 11776TriphenylphosphineHCID 221092-Bromo-4-nitrophenolHCID 680083-Fluorobenzylic alcoholHCID 5363146Diisopropyl azodicarboxylate

Product 1

HCID 218748002-Bromo-1-(3-fluorobenzyloxy)-4-nitrobenzeneYield 68%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

2-Bromo-4-nitrophenol (4.86 g, 0.0223 mol), triphenylphosphine (7.6 g, 0.0290 mol), 3-fluorobenzylalcohol (3.65 g, 0.0290 mol) were combined and dissolved in THF (89 mL). The reaction temperature was cooled to 0° C. and DIAD (4.50 g, 0.0290 mol) was added. The reaction was allowed to warm slowly to rt and stirred for 3 h before it was diluted with water (100 mL) and EtOAc (100 mL). The layers were separated and the aqueous layer was extracted with EtOAc (200 mL×2). The organic extracts were combined and washed with brine, followed by drying over sodium sulfate. The volatiles were removed in vacuo and the residual semi-solid was treated with diethyl ether. The solids were removed by filtration. The volatiles from the resulting filtrate were removed in vacuo and the material was purified using EtOAc:Hexanes (90/10) in a biotage LC system to afford the title compound as a yellow solid (3.73 g, 68% yield). 1H NMR (DMSO-d6) □ 8.43 (d, 1H); 8.26 (m, 1H); 7.45 (m, 1H); 7.38 (d, 1H); 7.30 (m, 2H); 7.17 (m, 1H); 5.39 (s, 2H).

Workup

  1. temperatureto warm slowly to rt
  2. customThe layers were separated
  3. extractionthe aqueous layer was extracted with EtOAc (200 mL×2)
  4. washwashed with brine
  5. dry with materialby drying over sodium sulfate
  6. customThe volatiles were removed in vacuo
  7. additionthe residual semi-solid was treated with diethyl ether
  8. customThe solids were removed by filtration
  9. customThe volatiles from the resulting filtrate were removed in vacuo
  10. customthe material was purified

Sources & evidence

ORD record
ord-5f82665f5b9e4376bb686e6d0cf1fc3d
Source dataset
uspto-grants-2007_03
Patent number
US07189734B2

Linked notes

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