Triphenylphosphine → 2-{2-bromo-4-fluoro-6-[(1E)-prop-1-enyl]phenoxy}but-3-enyl 4-methylbenzenesulfonate

HRID 902309Notes

Reaction equation

HRID 902309 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[C:4](/[CH:9]=[CH:10]/[CH3:11])[C:3]=1[OH:12].O[CH:14]([CH:27]=[CH2:28])[CH2:15][O:16][S:17]([C:20]1[CH:25]=[CH:24][C:23]([CH3:26])=[CH:22][CH:21]=1)(=[O:19])=[O:18].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>C1(C)C=CC=CC=1>[CH3:26][C:23]1[CH:24]=[CH:25][C:20]([S:17]([O:16][CH2:15][CH:14]([O:12][C:3]2[C:4](/[CH:9]=[CH:10]/[CH3:11])=[CH:5][C:6]([F:8])=[CH:7][C:2]=2[Br:1])[CH:27]=[CH2:28])(=[O:19])=[O:18])=[CH:21][CH:22]=1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 3557556(+-)-2-Hydroxy-3-buten-1-yl tosylateHCID 691167832-bromo-4-fluoro-6-[(1E)-prop-1-enyl]phenol

Product 1

HCID 866091062-{2-bromo-4-fluoro-6-[(1E)-prop-1-enyl]phenoxy}but-3-enyl 4-methylbenzenesulfonateYield 96.4%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

To a solution of 2-bromo-4-fluoro-6-[(1E)-prop-1-enyl]phenol (6.37 g, 0.0276 mol), toluene-4-sulfonic acid 2-hydroxy-but-3-enyl ester (8.8 g, 0.0363 mol) and triphenylphosphine (10.12 g, 0.0386 mol) in anhydrous toluene (200 mL) at 0° C. under nitrogen was added a solution of diethyl azodicarboxylate (6.72 g, 0.0386 mol) in anhydrous toluene (100 mL) over 10 minutes then the reaction mixture stirred at room temperature for 19 hours. The reaction was quenched by the addition of water (400 mL), stirred vigorously for 5 minutes and the resulting oily suspension extracted with diethyl ether (300 mL). The organic phase was separated, washed with water (2×500 mL), and saturated brine (400 mL), dried over magnesium sulfate, filtered and concentrated under reduced pressure to afford a yellow oil. Purification by flash chromatography using a solvent gradient of 2 to 10% ethyl acetate in hexane gave 12.11 g (96%) of 2-{2-bromo-4-fluoro-6-[(1E)-prop-1-enyl]phenoxy}but-3-enyl 4-methylbenzenesulfonate as a colorless oil. HRMS: calcd for C20H20BrFO4S+NH4+, 472.05879. found (ESI, [M+NH4]+), 472.0581.

Workup

  1. customThe reaction was quenched by the addition of water (400 mL)
  2. stirringstirred vigorously for 5 minutes
  3. extractionthe resulting oily suspension extracted with diethyl ether (300 mL)
  4. customThe organic phase was separated
  5. washwashed with water (2×500 mL), and saturated brine (400 mL)
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customto afford a yellow oil
  10. customPurification by flash chromatography

Sources & evidence

ORD record
ord-36970ea97ec94fd4a3eaa5889fd36c62
Source dataset
uspto-grants-2008_04
Patent number
US07365095B2

Reaction notes

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