Triphenylphosphine → HCID 11722548, compound

HRID 736607Notes

Reaction equation

HRID 736607 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[C:4]([F:9])[CH:3]=1.O[CH2:11][CH2:12][N:13]1[CH2:18][CH2:17][O:16][CH2:15][CH2:14]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>O1CCCC1>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][CH2:11][CH2:12][N:13]2[CH2:18][CH2:17][O:16][CH2:15][CH2:14]2)=[C:4]([F:9])[CH:3]=1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 611632-MorpholinoethanolHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 27249814-Bromo-2-fluorophenol

Product 1

HCID 11722548HCID 11722548, compoundYield 67.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

A mixture of 4-bromo-2-fluorophenol (0.612 g, 3.2 mmol; described: in Finger et al. J. Amer. Chem. Soc. 1959, 81, 94), 4-(2-hydroxyethyl)morpholine (0.47 ml, 3.84 mmol) and triphenylphosphine (1.0 g, 3.84 mmol) was dissolved in anhydrous tetrahydrofuran (5 mL) and cooled to 0° C. Diethyl azodicarboxylate (0.6 mL, 3.84 mmol) was added dropwise and the resulting mixture was stirred at room temperature for 3.5 h. The solvent was evaporated and the residue partioned between water and methylene chloride. The organic phase was washed twice with a saturated sodium hydrogen carbonate solution, dried (MgSO4) and the solvent was evaporated. The product was purified by column chromatography on silica using a gradient of toluene/acetonitrile, (4:1 to 0:1), as the eluent to give 0.655 g (67% yield) of the title compound as a clear oil: 1H NMR (CDCl3) δ 7.21 (d, J=11 Hz, 1H), 7.16 (m, 1H), 6.83 (t, J=9 Hz, 1H), 4.14 (t, J=6 Hz, 3H), 3.71 (t, J=5 Hz, 4H), 2.80 (t, J=6 Hz, 2H), (t, J=5 Hz, 4H); 13C NMR (CDCl3, 100) δ 154.2, 151.7, 146.5, 146.4, 127.4, 127.4, 120.1, 119.9, 116.8, 116.8, 112.7, 112.7, 68.1, 67.1, 57.6, 54.3; MS (ESP) m/z 304, 306 (M++1).

Workup

  1. customThe solvent was evaporated
  2. washThe organic phase was washed twice with a saturated sodium hydrogen carbonate solution
  3. dry with materialdried (MgSO4)
  4. customthe solvent was evaporated
  5. customThe product was purified by column chromatography on silica using a gradient of toluene/acetonitrile, (4:1 to 0:1), as the eluent

Sources & evidence

ORD record
ord-a59f2fc4bc7441e0b9c7234f28d0a0fd
Source dataset
uspto-grants-2009_09
Patent number
US07595319B2

Reaction notes

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