Water → HCID 11551291, compound

HRID 254240Notes

Reaction equation

HRID 254240 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][CH2:26][C:27]([CH3:31])(O)[CH:28]=[CH2:29].O>O1CCOCC1>[Cl:23][CH2:24][CH2:25][CH2:26][C:27]1([CH3:31])[CH2:28][CH2:29][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 14744900HCID 14744900, compound

Product 1

HCID 11551291HCID 11551291, compoundYield 49.3%

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 N2 atmosphere. A solution of 6-chloro-3-methyl-hex-1-en-3-ol (1.12 g, 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 removal of the solvents, the residue was mixed with methanol/HCl and let stand 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-(3-chloro-propyl)-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 removal of the solvents
  8. additionthe residue was mixed with methanol/HCl
  9. waitlet stand overnight at room temperature
  10. customAfter the removal of the solvents the residue
  11. customwas purified via flash column chromatography on silica gel (1:3 EtOAc/Hex) twice

Sources & evidence

ORD record
ord-76516631d41d4abb8bda1f11073d0e93
Source dataset
uspto-grants-2011_01
Patent number
US07875607B2

Reaction notes

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