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

HRID 1161455Notes

Reaction equation

HRID 1161455 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 reaction mixture 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 reaction mixture 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-9bdb45d9b4504a0ea4ad8f846873e2ee
Source dataset
uspto-grants-2010_10
Patent number
US07816522B2

Reaction notes

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