Water → HCID 11716671, compound

HRID 2378369Notes

Reaction equation

HRID 2378369 reaction equation
[CH:1]12[CH2:13][CH:4]([C:5]3[C:6]([OH:12])=[CH:7][CH:8]=[C:9]([OH:11])[C:10]=31)[CH2:3][CH2:2]2.B(F)(F)F.[CH3:18]COCC.[CH3:23][C:24]1([CH:30]=[CH2:31])[O:28][C:27](=[O:29])[CH2:26][CH2:25]1.O>O1CCOCC1>[CH3:18][O:28][C:27](=[O:29])[CH2:26][CH2:25][C:24]1([CH3:23])[CH2:30][CH2:31][C:7]2[C:6](=[C:5]3[CH:4]4[CH2:13][CH:1]([CH2:2][CH2:3]4)[C:10]3=[C:9]([OH:11])[CH:8]=2)[O:12]1

Participants

6

Reactant 4

HCID 962WaterHCID 8000Boron trifluoride etherateHCID 859671,4-Methanonaphthalene-5,8-diol, 1,2,3,4-tetrahydro-HCID 1025504-HYDROXY-4-METHYL-5-HEXENOIC ACID gamma LACTONE

Product 1

HCID 11716671HCID 11716671, compoundYield 103.5%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent2×

Conditions

Temperature
110 °C

Procedure

A mixture of 1,2,3,4-tetrahydro-1,4-methano-naphthalene-5,8-diol (1.34 g, 7.94 mmol), 1.0 mL (3.97 mmol) of BF3.Et2O and 25 mL of dioxane was heated up to 110° C. under a nitrogen atmosphere. A solution of 5-methyl-5-vinyl-dihydro-furan-2-one (1.12 mg, 8.6 mmol) in 24 ml of dioxane was added slowly to the mixture. The addition was completed after two hours and the mixture was continued to reflex for additional 3 hours. After cooling down to room temperature, the mixture was poured to water, extracted with ethyl acetate, washed with water and dried over MgSO4. After the removal of solvents, the residue was mixed with methanol/HCl and let stand overnight at room temperature. Then the solvents were removed and the residue was purified via flash column chromatography on silica gel (1:3 EtOAc/Hex) twice to give 1.30 g of 3-(6-hydroxy-2-methyl-3,4,7,8,9,10-hexahydro-7,10-methano-2H-benzo[h]chromen-2-yl)-propionic acid methyl ester. 1H-NMR (300 MHz, CDCl3) δ (ppm): 6.29 (s. 1H), 4.70 (s, 1H), 3.68 (s, 3H), 3.52-3.46 (d, 2H), 2.69-2.55 (m, 2H), 2.52-2.47 (m, 2H), 2.00-1.64 (m, 8H), 1.43-1.15 (m, 5H). MS (ESI): 317 (M+H+, 70%), 339 (M+Na+, 100%).

Workup

  1. additionThe addition
  2. waitto reflex for additional 3 hours
  3. temperatureAfter cooling down to room temperature
  4. extractionextracted with ethyl acetate
  5. washwashed with water
  6. dry with materialdried over MgSO4
  7. customAfter the removal of solvents
  8. additionthe residue was mixed with methanol/HCl
  9. waitlet stand overnight at room temperature
  10. customThen the solvents were removed
  11. customthe residue was purified via flash column chromatography on silica gel (1:3 EtOAc/Hex) twice

Sources & evidence

ORD record
ord-1e9b9963e59d4c39a190681445767aa0
Source dataset
uspto-grants-2008_12
Patent number
US07470798B2

Reaction notes

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