Potassium Hydroxide → 5-Methoxytricyclo[7.2.1.02,7]dodeca-2(7),3,5,10-tetraene

HRID 990750Notes

Reaction equation

HRID 990750 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[CH:5][C:6]2[CH:7]3[CH2:15][CH:10]([C:11](=O)[C:12]=2[CH:13]=1)[CH:9]=[CH:8]3.[OH-].[K+].O.NN>C(O)CO>[CH3:1][O:2][C:3]1[CH:4]=[CH:5][C:6]2[CH:7]3[CH2:15][CH:10]([CH2:11][C:12]=2[CH:13]=1)[CH:9]=[CH:8]3

Participants

5

Reactant 3

HCID 14797Potassium HydroxideHCID 24654Hydrazine hydrate (1:1)HCID 18415737HCID 18415737, compound

Product 1

HCID 184157365-Methoxytricyclo[7.2.1.02,7]dodeca-2(7),3,5,10-tetraene

Reagents, catalysts & solvents 1

HCID 174Ethylene GlycolSolvent

Procedure

5-Methoxytricyclo[7.2.1.02,7]dodeca-2(7),3,5,10-tetraene-8-one (9.41 g, 47 mmol) and pulverized potassium hydroxide (KOH) (6.17 g, 110 mmol) were warmed in ethylene glycol (50 mL) until solution occurred. The mixture was cooled to rt, treated with hydrazine hydrate (6 mL, 190 mmol) and heated to reflux for 2 hours. The reflux condenser was replaced with a distilling head and distillates were collected from 120-190° C. The distillates were diluted with H2O (100 mL) and extracted with EtOAc (4×40 mL). The organic layer was washed with H2O (4×30 mL), brine (25 mL), dried (MgSO4), filtered and concentrated to an oil (8.2 g, 94%). (TLC 25%EtOAc/hexanes Rf 0.68). 1H NMR (CDCl3) δ6.92 (d, J=8.0 Hz, 1H), 6.88 (m, 2H), 6.25 (dd, J=5.1,2.5 Hz, 1H), 5.79 (dd, J=5.1,2.4 Hz, 1H), 3.77 (s, 3H), 3.31 (br s, 1H), 3.01-2.94 (2H), 2.56 (d, J=16.5 Hz, 1H), 2.22 (m, 1H), 1.85 (d, J=10.0 Hz, 1H). GCMS m/e 186 (M+).

Workup

  1. temperatureheated
  2. temperatureto reflux for 2 hours
  3. customwere collected from 120-190° C
  4. additionThe distillates were diluted with H2O (100 mL)
  5. extractionextracted with EtOAc (4×40 mL)
  6. washThe organic layer was washed with H2O (4×30 mL), brine (25 mL)
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated to an oil (8.2 g, 94%)

Sources & evidence

ORD record
ord-ddf2d2e8117c44b1aff2657ce0c0e960
Source dataset
uspto-grants-2002_10
Patent number
US06462035B1

Reaction notes

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