Triphenylphosphine → Ethyl 3-[2-(2-fluorophenyl)-vinyl]-4-methoxybenzoate

HRID 558414

Reaction equation

HRID 558414 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[F:20][C:21]1[CH:28]=[CH:27][CH:26]=[CH:25][C:22]=1[CH2:23]Br.[CH:29]([C:31]1[CH:32]=[C:33]([CH:39]=[CH:40][C:41]=1[O:42][CH3:43])[C:34]([O:36][CH2:37][CH3:38])=[O:35])=O.C[O-].[Na+]>C(OCC)(=O)C.CO.CN(C)C=O>[F:20][C:21]1[CH:28]=[CH:27][CH:26]=[CH:25][C:22]=1[CH:23]=[CH:29][C:31]1[CH:32]=[C:33]([CH:39]=[CH:40][C:41]=1[O:42][CH3:43])[C:34]([O:36][CH2:37][CH3:38])=[O:35]

Participants

8

Reactant 4

HCID 11776TriphenylphosphineHCID 67968alpha-Bromo-o-fluorotolueneHCID 638670Ethyl 3-formyl-4-methoxybenzoateHCID 10942334Sodium Methoxide

Product 1

HCID 67002085Ethyl 3-[2-(2-fluorophenyl)-vinyl]-4-methoxybenzoateYield 80%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

N,N-Dimethylformamide (5 mL) was added to 1.0 g of polymer-supported triphenylphosphine (produced by Fluka, CAS registry number 39319-11-4) and 1.1 g of 2-fluorobenzyl bromide, and the mixture was stirred for 10 hours at 80° C. The reaction mixture was filtered, and then washed with N,N-dimethylformamide, dichloromethane, and methanol. The residue was dried under reduced pressure to prepare polymer-supported (2-fluorobenzyl)-triphenylphosphonium bromide. This product (144 mg) was added to a methanol solution (2 mL) of 30 mg of ethyl 3-formyl-4-methoxybenzoate obtained in step C of Example 1-2-1. After 80 μL of 28% sodium methoxide was added, the reactor was sealed, and the mixture was stirred for 4 hours at 70° C. The residue was diluted with ethyl acetate, washed with purified water, and dried over anhydrous sodium sulfate. The anhydrous sodium sulfate was separated by filtration, and then the filtrate was concentrated under reduced pressure. The residue was dried under reduced pressure to obtain 33 mg (80%) of ethyl 3-[2-(2-fluorophenyl)-vinyl]-4-methoxybenzoate.

Workup

  1. filtrationThe reaction mixture was filtered
  2. washwashed with N,N-dimethylformamide, dichloromethane, and methanol
  3. customThe residue was dried under reduced pressure
  4. customto prepare polymer-supported (2-fluorobenzyl)-triphenylphosphonium bromide
  5. customthe reactor was sealed
  6. stirringthe mixture was stirred for 4 hours at 70° C
  7. washwashed with purified water
  8. dry with materialdried over anhydrous sodium sulfate
  9. customThe anhydrous sodium sulfate was separated by filtration
  10. concentrationthe filtrate was concentrated under reduced pressure
  11. customThe residue was dried under reduced pressure

Sources & evidence

ORD record
ord-184780b3ef50493d9036ea9668845aed
Source dataset
uspto-grants-2011_11
Patent number
US08063046B2

Linked notes

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