Triphenylphosphine → [4-(Ethoxycarbonyl)-2-fluorobenzyl](triphenyl)phosphonium bromide

HRID 1465485Notes

Reaction equation

HRID 1465485 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([CH:10]=[CH:11][C:12]=1[CH3:13])[C:5]([O:7][CH2:8][CH3:9])=[O:6].[Br:14]N1C(=O)CCC1=O.[C:22]1([P:28]([C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)[C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1>C(Cl)(Cl)(Cl)Cl.N(C(C)(C)C#N)=NC(C)(C)C#N>[Br-:14].[CH2:8]([O:7][C:5]([C:4]1[CH:10]=[CH:11][C:12]([CH2:13][P+:28]([C:29]2[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=2)([C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)[C:22]2[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=2)=[C:2]([F:1])[CH:3]=1)=[O:6])[CH3:9]

Participants

6

Reactant 3

HCID 11776TriphenylphosphineHCID 67184N-bromobutanimideHCID 13489923Benzoic acid, 3-fluoro-4-methyl-, ethyl ester

Product 1

HCID 86651846[4-(Ethoxycarbonyl)-2-fluorobenzyl](triphenyl)phosphonium bromideYield 83.7%

Reagents, catalysts & solvents 2

HCID 6547AzobisisobutyronitrileCatalystHCID 5943Carbon TetrachlorideSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of ethyl 3-fluoro-4-methylbenzoate (8.586 g, 47.13 mmol) in carbon tetrachloride (70 ml) were added N-bromosuccinimide (8.388 g, 47.13 mmol) and 2,2′-azobisisobutyronitrile (309.6 mg, 1.885 mmol), and the mixture was stirred at 90° C. for 30 mins and at 100° C. for 16 hrs. The reaction mixture was cooled to 0° C., and the precipitated solid was filtered off and washed twice with hexane. The filtrate and washing solution were combined, and the mixture was washed twice with water and once with saturated brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was dissolved in toluene (30 ml), and triphenylphosphine (9.891 g, 37.71 mmol) was added. The mixture was heated under reflux for 40 mins and cooled to room temperature. The precipitate was collected by filtration, and dried under reduced pressure to give [4-(ethoxycarbonyl)-2-fluorobenzyl](triphenyl)phosphonium bromide (16.52 g, yield 67.0%) as a white solid.

Workup

  1. temperatureThe reaction mixture was cooled to 0° C.
  2. filtrationthe precipitated solid was filtered off
  3. washwashed twice with hexane
  4. washThe filtrate and washing solution
  5. washthe mixture was washed twice with water and once with saturated brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. concentrationconcentrated under reduced pressure
  8. dissolutionThe residue was dissolved in toluene (30 ml)
  9. temperatureThe mixture was heated
  10. temperatureunder reflux for 40 mins
  11. temperaturecooled to room temperature
  12. filtrationThe precipitate was collected by filtration
  13. customdried under reduced pressure

Sources & evidence

ORD record
ord-c422ff8df99c4b988297f538ba8414e2
Source dataset
uspto-grants-2015_04
Patent number
US08999989B2

Reaction notes

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