Sodium Hydroxide → 2-Phenylhexahydro-2,5-methanopentalene-3a-carboxylic acid

HRID 2405696Notes

Reaction equation

HRID 2405696 reaction equation
[OH-].[Na+].BrBr.[C:5]1([C:11]23[CH2:22][CH:15]4[CH2:16][C:17]([C:19](=[O:21])C)([CH2:18]2)[CH:13]([CH2:14]4)[CH2:12]3)[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1.C[O:24]C(C)(C)C>O.O1CCOCC1>[C:5]1([C:11]23[CH2:22][CH:15]4[CH2:16][C:17]([C:19]([OH:24])=[O:21])([CH2:18]2)[CH:13]([CH2:14]4)[CH2:12]3)[CH:6]=[CH:7][CH:8]=[CH:9][CH:10]=1

Participants

7

Reactant 4

HCID 14798Sodium HydroxideHCID 15413tert-Butyl methyl etherHCID 24408BromineHCID 593749561-(2-Phenylhexahydro-2,5-methanopentalen-3a-yl)ethanone

Product 1

HCID 673007182-Phenylhexahydro-2,5-methanopentalene-3a-carboxylic acid

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 312751,4-DioxaneSolvent2×

Procedure

Dioxane (1.81) was added to a solution, cooled to −22° C., of sodium hydroxide (724 g) in water (4.8 l). Bromine (578 g) was metered into this solution such that a temperature of −15° C. was not exceeded. A solution of 1-(2-phenylhexahydro-2,5-methanopentalen-3a-yl)ethanone (290 g) in dioxane (600 ml) was metered into this solution, and the reaction was allowed to warm up gradually to room temperature. tert-Butyl methyl ether was added. Subsequently, water was metered in (2.5 l). After phase separation, the aqueous phase was washed with tert-butyl methyl ether. Subsequently, after addition of tert-butyl methyl ether (5 l), hydrochloric acid (32%) was used to establish a pH of pH 1.5. After phase separation, the organic phase was washed repeatedly with water and clarified with activated carbon. The solvent was changed by distillation under reduced pressure with addition of diisopropyl ether. After extractive stirring with diisopropyl ether at reflux, 2-phenylhexahydro-2,5-methanopentalene-3a-carboxylic acid (292 g) was obtained as a solid with 95% purity.

Workup

  1. customwas metered into this solution such that a temperature of −15° C.
  2. customAfter phase separation
  3. washthe aqueous phase was washed with tert-butyl methyl ether
  4. additionSubsequently, after addition of tert-butyl methyl ether (5 l), hydrochloric acid (32%)
  5. customAfter phase separation
  6. washthe organic phase was washed repeatedly with water
  7. distillationThe solvent was changed by distillation under reduced pressure with addition of diisopropyl ether
  8. temperatureat reflux

Sources & evidence

ORD record
ord-9f9105e73e984478bfb75b29677988ab
Source dataset
uspto-grants-2014_08
Patent number
US08809324B2

Reaction notes

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