Ammonium Chloride → 3-Fluoro-6-methoxy-2-vinylphenol

HRID 1698705Notes

Reaction equation

HRID 1698705 reaction equation
[CH2:1]([Li])CCC.[F:6][C:7]1[C:12]([CH:13]=O)=[C:11]([OH:15])[C:10]([O:16][CH3:17])=[CH:9][CH:8]=1.[Cl-].[NH4+]>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1(C)C=CC=CC=1>[F:6][C:7]1[C:12]([CH:13]=[CH2:1])=[C:11]([OH:15])[C:10]([O:16][CH3:17])=[CH:9][CH:8]=1

Participants

6

Reactant 3

HCID 25517Ammonium ChlorideHCID 224828186-Fluoro-2-hydroxy-3-methoxybenzaldehydeHCID 178418339Butyllithium

Product 1

HCID 670973333-Fluoro-6-methoxy-2-vinylphenol

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 1140TolueneSolvent2×

Procedure

To a suspension of 50 g of methyltriphenylphosphonium bromide in 300 ml of toluene there was added 45 ml of n-butyllithium (2.55 M, hexane solution) while cooling on ice under a nitrogen atmosphere. After stirring at room temperature for 2 hours, the reaction mixture was allowed to stand. A 150 ml portion of the supernatant was added dropwise to a solution of 5.00 g of 6-fluoro-2-hydroxy-3-methoxybenzaldehyde [CAS No. 457628-15-8] in 90 ml of toluene while cooling on ice. After stirring the mixture at room temperature for 1 hour, saturated aqueous ammonium chloride was added to the reaction mixture. The organic layer was extracted with ethyl acetate The organic layer was dried over anhydrous magnesium sulfate. The desiccating agent was filtered off and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate-heptane) to give 3-fluoro-6-methoxy-2-vinylphenol (4.33 g) as a solid.

Workup

  1. temperaturewhile cooling on ice under a nitrogen atmosphere
  2. stirringAfter stirring the mixture at room temperature for 1 hour
  3. extractionThe organic layer was extracted with ethyl acetate The organic layer
  4. dry with materialwas dried over anhydrous magnesium sulfate
  5. filtrationThe desiccating agent was filtered off
  6. concentrationthe filtrate was concentrated under reduced pressure
  7. customThe residue was purified by silica gel column chromatography (ethyl acetate-heptane)

Sources & evidence

ORD record
ord-0665de4c8b994965b55b873e4e0e18d6
Source dataset
uspto-grants-2012_04
Patent number
US08163787B2

Reaction notes

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