Acetic Acid → 2-Phenylhexahydro-2,5-methanopentalene-3a-carboxylic acid

HRID 1015567Notes

Reaction equation

HRID 1015567 reaction equation
[OH-].[Na+].BrBr.Br[O-].[C:7]1([C:13]23[CH2:21][CH:17]4C[CH:19]([CH2:20]2)[C:15](C(=O)C)([CH2:16]4)[CH2:14]3)[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.[CH3:25][C:26]([OH:28])=[O:27]>O1CCOCC1.O>[C:7]1([C:13]23[CH2:14][CH:15]4[CH2:16][CH:17]([CH2:21]2)[C:25]([C:26]([OH:28])=[O:27])([CH2:19]4)[CH2:20]3)[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1

Participants

8

Reactant 5

HCID 176Acetic AcidHCID 14798Sodium HydroxideHCID 24408BromineHCID 5460626HypobromiteHCID 593749561-(2-Phenylhexahydro-2,5-methanopentalen-3a-yl)ethanone

Product 1

HCID 673007182-Phenylhexahydro-2,5-methanopentalene-3a-carboxylic acidYield 64%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 312751,4-DioxaneSolvent2×

Procedure

To a stirred mixture of NaOH (2.4 g, 60.0 mmol), H2O (16 mL), and 1,4 dioxane (2 mL) at ice bath temperature was added Br2 (0.56 mL, 10.4 mmol) and stirred for 15 minutes. The resulting hypobromite solution was added dropwise to a stirred solution of 1-(1-phenyltricyclo[3.3.1.03,7]non-3-yl)ethanone obtained from preparation I (1.0 g, 4.0 mmol) in 1,4-dioxane (6 mL) at ice bath temperature. After stirring the reaction mixture at r.t. for 1 h, it was again cooled to ice bath temperature and quenched by adding AcOH (3.6 mL, 60 mmol). The reaction mixture was diluted with water and extracted with EtOAc. The combined organic layer was washed with brine, dried over Na2SO4, and the solvent was removed under reduced pressure to obtain 1-phenyltricyclo[3.3.1.03,7]nonane-3-carboxylic acid (0.62 g) in 64% yield. m/z (M+1) 243; 1H NMR (CDCl3) 300 MHz δ 7.40-7.25 (m, 4H), 7.25-7.18 (m, 1H), 2.90-2.86 (m, 1H), 2.54-2.48 (m, 1H), 2.38 (ddd, J=2.0, 2.0, 11.0 Hz, 1H), 2.20-2.05 (m, 4H), 1.98-1.78 (m, 5H), 1.70 (dd, J=2.8, 11.5 Hz, 1H).

Workup

  1. stirringAfter stirring the reaction mixture at r.t. for 1 h
  2. temperatureit was again cooled to ice bath temperature
  3. customquenched
  4. extractionextracted with EtOAc
  5. washThe combined organic layer was washed with brine
  6. dry with materialdried over Na2SO4
  7. customthe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-d44fc4896ca64a8898fa89e55ecfa94e
Source dataset
uspto-grants-2011_07
Patent number
US07985759B2

Reaction notes

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