Dibenzosuberone → 5-Cyclopropyl-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ol

HRID 1046725Notes

Reaction equation

HRID 1046725 reaction equation
[Mg].[CH:2]1(Br)[CH2:4][CH2:3]1.[CH:6]1[C:16]2[CH2:15][CH2:14][C:13]3[CH:17]=[CH:18][CH:19]=[CH:20][C:12]=3[C:11](=[O:21])[C:10]=2[CH:9]=[CH:8][CH:7]=1.[Cl-].[NH4+].O>C1COCC1>[CH:2]1([C:11]2([OH:21])[C:12]3[CH:20]=[CH:19][CH:18]=[CH:17][C:13]=3[CH2:14][CH2:15][C:16]3[CH:6]=[CH:7][CH:8]=[CH:9][C:10]2=3)[CH2:4][CH2:3]1

Participants

6

Reactant 4

HCID 14589DibenzosuberoneHCID 78037BromocyclopropaneHCID 5462224MagnesiumHCID 57429219Ammonium chloride monohydrate

Product 1

HCID 192613825-Cyclopropyl-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-olYield 52%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
60 °C

Procedure

In a three neck round bottom flask equipped with stirrer, (0.243 g, 0.009 mol) of magnesium turnings and 2.5 mL of dry THF was added. The reaction was stirred to allow the metal to dissolve. At this point the temperature was raised to 60° C. and cyclopropyl bromide (1.21 g, 0.010 mol) was added dropwise. The reaction mixture was allowed to reflux for 1.5 h at 70° C. and then lowered to 60° C. Then (1.04 g, 0.005 mol) of 10,11-dihydro-dibenzo[a,d]cyclohepten-5-one was added dropwise. Upon addition, the solution turned purple in color. The temperature was raised to 70° C. after addition was complete. The reaction refluxed for an additional 2 h and HPLC was used to monitor reaction progress. Ammonium chloride/H2O (7.5 mL) was added to quench the reaction and the flask placed in an ice bath. The resulting solution was filtered and the filtrate was transferred to a 250-mL separatory funnel charged with DCM (100 mL). Then finally NaCl/H2O solution (80 mL) was added. The organic phase was removed and dried over Na2SO4 for 2 h. The solvent was removed under reduced pressure and the product was dried under vacuum overnight. 1H NMR and LC/MS confirmed the product. (Yield ˜52%).

Workup

  1. customIn a three neck round bottom flask equipped with stirrer
  2. dissolutionto dissolve
  3. temperatureto reflux for 1.5 h at 70° C.
  4. customlowered to 60° C
  5. additionUpon addition
  6. temperatureThe temperature was raised to 70° C.
  7. additionafter addition
  8. temperatureThe reaction refluxed for an additional 2 h
  9. customreaction progress
  10. customto quench
  11. customthe reaction
  12. customthe flask placed in an ice bath
  13. filtrationThe resulting solution was filtered
  14. customthe filtrate was transferred to a 250-mL separatory funnel
  15. additioncharged with DCM (100 mL)
  16. additionThen finally NaCl/H2O solution (80 mL) was added
  17. customThe organic phase was removed
  18. dry with materialdried over Na2SO4 for 2 h
  19. customThe solvent was removed under reduced pressure
  20. customthe product was dried under vacuum overnight

Sources & evidence

ORD record
ord-06c2046f041e46c8a1cb1701402d4098
Source dataset
uspto-grants-2013_10
Patent number
US08569380B2

Reaction notes

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