Allyl bromide → 9-(Prop-2-en-1-yl)-9H-fluorene-9-carboxylic acid

HRID 1836836Notes

Reaction equation

HRID 1836836 reaction equation
[CH2:1]([Li])[CH2:2][CH2:3]C.[CH:6]1[C:18]2[CH:17]([C:19]([OH:21])=[O:20])[C:16]3[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=3)[C:10]=2[CH:9]=[CH:8][CH:7]=1.C(Br)C=C.[Cl-].[NH4+]>C1COCC1.C(OCC)(=O)C>[CH2:3]([C:17]1([C:19]([OH:21])=[O:20])[C:18]2[CH:6]=[CH:7][CH:8]=[CH:9][C:10]=2[C:11]2[C:16]1=[CH:15][CH:14]=[CH:13][CH:12]=2)[CH:2]=[CH2:1]

Participants

7

Reactant 4

HCID 7841Allyl bromideHCID 25517Ammonium ChlorideHCID 748099-Carboxyfluorene2×HCID 178418339Butyllithium

Product 1

HCID 142239519-(Prop-2-en-1-yl)-9H-fluorene-9-carboxylic acid

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

Procedure

n-Butyllithium (1.50 mol/l, n-hexane solution) was slowly added dropwise to a solution of fluorene-9-carboxylic acid (3.0 g) in THF in an argon atmosphere at −78° C. The mixture was stirred at −78° C. for 30 min and then at 0° C. for 30 min. The stirred mixture was again cooled to −78° C. Allyl bromide (2.5 ml) was slowly added dropwise thereto at −78° C., and the mixture was stirred at −78° C. for 30 min and then at room temperature overnight. After the disappearance of fluorene-9-carboxylic acid was confirmed by TLC, a saturated aqueous ammonium chloride solution was slowly added to the reaction solution. Ethyl acetate was then added thereto to perform extraction. The organic layer was washed with a saturated aqueous sodium chloride solution and was then dried over anhydrous magnesium sulfate. The solvent was removed by distillation under the reduced pressure. The residue was purified by column chromatography on silica gel (dichloromethane:methanol=20:1) to give 9-allyl-9H-fluorene-9-carboxylic acid (3.58 g) as a white solid.

Workup

  1. waitat 0° C. for 30 min
  2. temperatureThe stirred mixture was again cooled to −78° C
  3. stirringat −78° C., and the mixture was stirred at −78° C. for 30 min
  4. customat room temperature
  5. customovernight
  6. extractionextraction
  7. washThe organic layer was washed with a saturated aqueous sodium chloride solution
  8. dry with materialwas then dried over anhydrous magnesium sulfate
  9. customThe solvent was removed by distillation under the reduced pressure
  10. customThe residue was purified by column chromatography on silica gel (dichloromethane:methanol=20:1)

Sources & evidence

ORD record
ord-8b28655f55c7449685c1e6c1d0f4eb78
Source dataset
uspto-grants-2004_08
Patent number
US06777414B1

Reaction notes

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