Chloroacetic Acid → {[2-(Bicyclo[2.2.1]hept-5-en-2-yl)propan-2-yl]oxy}acetic acid

HRID 229316Notes

Reaction equation

HRID 229316 reaction equation
[CH:1]12[CH2:7][CH:4]([CH:5]=[CH:6]1)[CH2:3][CH:2]2[C:8]([OH:11])([CH3:10])[CH3:9].C([Li])CCC.Cl[CH2:18][C:19]([OH:21])=[O:20].O>C1(C)C=CC=CC=1>[CH:1]12[CH2:7][CH:4]([CH:5]=[CH:6]1)[CH2:3][CH:2]2[C:8]([O:11][CH2:18][C:19]([OH:21])=[O:20])([CH3:9])[CH3:10]

Participants

6

Reactant 4

HCID 300Chloroacetic AcidHCID 962WaterHCID 4288842-(5-bicyclo[2.2.1]hept-2-enyl)propan-2-olHCID 178418339Butyllithium2×

Product 1

HCID 59000317{[2-(Bicyclo[2.2.1]hept-5-en-2-yl)propan-2-yl]oxy}acetic acidYield 31.4%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

2-(5-norbornen-2-yl)-2-propanol (15.20 g, 0.10 mole) (JSR Corp., Japan) and toluene (100 ml) were added to a three-necked 500 ml round bottomed flask equipped with a magnetic stirrer, an addition funnel, and a condenser with a nitrogen inlet. The addition funnel was charged with n-butyl lithium (1.6M in hexane, 62.50 ml, 0.10 mole). The n-butyl lithium was added drop wise while stirring at room temperature. An exothermic reaction occurred. Afterwards, chloroacetic acid (4.75 g, 0.05 mole) in toluene (100 ml) was added drop wise. The contents were heated to reflux for about 20 hours. After cooling to room temperature, water (200 ml) was added cautiously and stirred. The water phase was collected, washed with ether (100 ml) and neutralized with 2 molar hydrochloric acid solution. The cloudy solution was extracted twice with ether (100 ml) and the combined ether solutions was washed with brine (100 ml) and dried over anhydrous magnesium sulfate. The solvent was removed and the residue was recrystallized from a small amount of hexane to give 3.3 g of white crystalline material (Melting Point: 48.5-49.50° C.).

Workup

  1. customequipped with a magnetic stirrer, an addition funnel, and a condenser with a nitrogen inlet
  2. customAn exothermic reaction
  3. temperatureThe contents were heated
  4. temperatureto reflux for about 20 hours
  5. temperatureAfter cooling to room temperature
  6. stirringstirred
  7. customThe water phase was collected
  8. washwashed with ether (100 ml)
  9. extractionThe cloudy solution was extracted twice with ether (100 ml)
  10. washthe combined ether solutions was washed with brine (100 ml)
  11. dry with materialdried over anhydrous magnesium sulfate
  12. customThe solvent was removed
  13. customthe residue was recrystallized from a small amount of hexane

Sources & evidence

ORD record
ord-6ccbf64be01f4404a5577e18a0fb42c2
Source dataset
uspto-grants-2009_07
Patent number
US07563558B2

Reaction notes

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