Potassium Hydroxide → HCID 67793788, compound

HRID 1651061Notes

Reaction equation

HRID 1651061 reaction equation
[Br:1][C:2]1[CH:28]=[CH:27][C:5]2C(COS(C3C=CC(C)=CC=3)(=O)=O)[C:7]3[CH:14]=[CH:13][CH:12]=[CH:11][C:8]=3[CH:9]=[CH:10][C:4]=2[CH:3]=1.[C:29]([O-:32])(=O)[CH3:30].[Na+].[OH-].[K+]>C(O)(=O)C.CO>[Br:1][C:2]1[CH:28]=[CH:27][C:5]2[C:29]([OH:32])=[CH:30][C:7]3[CH:14]=[CH:13][CH:12]=[CH:11][C:8]=3[CH:9]=[CH:10][C:4]=2[CH:3]=1

Participants

6

Reactant 3

HCID 14797Potassium HydroxideHCID 517045Sodium AcetateHCID 86743949HCID 86743949, compound

Product 1

HCID 67793788HCID 67793788, compoundYield 47.7%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 887MethanolSolvent

Procedure

To a solution of 2-bromo-5-p-toluenesulphonyloxymethyl-dibenzo[a,d]cycloheptene (8.1 g) in glacial acetic acid (75 ml) was added anhydrous sodium acetate (2.9 g). The reaction mixture was refluxed for 24 h then the solvent removed under vacuum to leave a residue which was partitioned between dichloromethane (3×100 ml) and water (100 ml). The combined organic layers were dried (Na2SO4) , filtered and concentrated in vacuo to leave a residue which was dissolved in 75% aqueous methanol (100 ml) and treated with potassium hydroxide (4 g). After 14 h the reaction mixture was concentrated in vacuo and the residue partitioned between water (50 ml) and diethyl ether (3×50 ml). The combined organic layers were dried (Na2SO4) , filtered and concentrated in vacuo. Chromatography of the residue on flash silica with 10% ethyl acetate in hexane as eluent gave the less polar isomer, 2-bromo-5-hydroxy-dibenzo[a,e]cyclooctene (2.54 g, m.p. 148°-151° C.). δ (360 MHz, CDCl3) 3.26 (1H, dd, J=13.9 and 9.9 Hz, CHAHB --CHOH), 3.46 (1H, dd, J=13.9 and 6.2 Hz, CHAHB --CHOH), 5.24 (1H, dd, J=9.9 and 6.2 Hz, CHOH), 6.76 (1H, d, J=12.1 Hz, CHC =CHD), 6.87 (1H, d, J=12.1 Hz, CHC =CHD), 7.09-7.35 (7H, m, ArH), m/e 302 and 300 (M+); and as an oil the more polar isomer 2-bromo-6-hydroxy-dibenzo[a,e]cyclooctene (1.04 g), 67 (360 MHz, CDCl3) 3.25 (1H, dd, J=13.8 and 10.0 Hz CHAHB --CHOH), 3.40 (1H, dd, J=13.8 and 6.4 Hz, CHAHB --CHOH), 5.26 (1H, dd, J =10.0 and 6.4 Hz, CHAHB --CHOH), 6.75 (1H, d, J=12.1 Hz, CHC =CHD), 6.90 (1H, d, J=12.1 Hz, CHC =CHD), 7.08-7.45 (7H, m, ArH). m/e 302 and 300 (M+).

Workup

  1. temperatureThe reaction mixture was refluxed for 24 h
  2. customthe solvent removed under vacuum
  3. customto leave a residue which
  4. customwas partitioned between dichloromethane (3×100 ml) and water (100 ml)
  5. dry with materialThe combined organic layers were dried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customto leave a residue which
  9. concentrationAfter 14 h the reaction mixture was concentrated in vacuo
  10. customthe residue partitioned between water (50 ml) and diethyl ether (3×50 ml)
  11. dry with materialThe combined organic layers were dried (Na2SO4)
  12. filtrationfiltered
  13. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-5f52c4bfea124b3ead648e27fd6567fe
Source dataset
uspto-grants-1990_05
Patent number
US04927819

Reaction notes

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