Water → HCID 11601755, compound

HRID 2378377Notes

Reaction equation

HRID 2378377 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.CCOCC.[Cl:23][CH2:24][CH2:25][C:26]([CH3:30])(O)[CH:27]=[CH2:28].O>O1CCOCC1>[Cl:23][CH2:24][CH2:25][C:26]1([CH3:30])[CH2:27][CH2:28][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 21494880HCID 21494880, compound

Product 1

HCID 11601755HCID 11601755, compoundYield 51.6%

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, 794 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-chloro-3-methyl-pent-1-en-3-ol (1.12g, 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 reflux for an 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 stirred overnight at room temperature. After the removal of the solvents the residue was purified via flash column chromatography on silica gel (1:3 EtOAc/Hex) twice to give 1.30 g of 2-(2-chloro-ethyl)-2-methyl-3,4,7,8,9,10-hexahydro-7,10-methano-2H-benzo[h]chromen-6-ol. 1H-NMR (300 MHz, CDCl3) δ (ppm): 6.39 (s, 1H), 4.27 (s, 1H), 3.63-3.47 (m, 4H), 2.73-2.70 (m, 2H), 2.00-1.47 (m, 8H), 1.43-1.15 (m, 4H); MS: 307 (M+H+, 100%).

Workup

  1. additionThe addition
  2. temperatureto reflux for an 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. customAfter the removal of the solvents the residue
  10. customwas purified via flash column chromatography on silica gel (1:3 EtOAc/Hex) twice

Sources & evidence

ORD record
ord-7d0bc920f0034dc5a771df1da68a4eaa
Source dataset
uspto-grants-2008_12
Patent number
US07470798B2

Reaction notes

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