Acetic Acid → HCID 68425498, compound

HRID 1527831Notes

Reaction equation

HRID 1527831 reaction equation
[CH:1]1([C:4]2(O)[C:10]3[CH:11]=[CH:12][CH:13]=[CH:14][C:9]=3C=C(N3CCCCC3)[C:6]3[CH:21]=[CH:22][CH:23]=[CH:24][C:5]2=3)[CH2:3][CH2:2]1.[BrH:26].[C:27]([OH:30])(=O)[CH3:28]>C(#N)C>[Br:26][CH2:3][CH2:2][CH:1]=[C:4]1[C:10]2[CH:11]=[CH:12][CH:13]=[CH:14][C:9]=2[CH2:28][C:27](=[O:30])[C:6]2[CH:21]=[CH:22][CH:23]=[CH:24][C:5]1=2

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 260Hydrogen BromideHCID 103593635-Cyclopropyl-10-(1-piperidinyl)-5H-dibenzo[a,d]cyclohepten-5-ol

Product 1

HCID 68425498HCID 68425498, compound

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
100 °C

Procedure

5-Cyclopropyl-10-piperidin-1-yl-5H-dibenzo[a,d]cyclohepten-5-ol (5) (69 mmol, 1.00 equiv.) was dissolved in 100 mL acetic acid, then 48% aqueous HBr (100 mL) was added and the resulting mixture was heated in a 100° C. oil bath. LC/MS analysis after 18 hours showed that the starting material was consumed. The mixture was diluted with H2O (100 mL) then extracted in a separatory funnel with ethyl ether (3×100 mL). The aqueous phase was discarded, after which the combined organic phases were washed with saturated sodium bicarbonate (3×50 mL). The aqueous phase was discarded, and the organic phase was filtered through a silica gel plug and concentrated under vacuum to obtain a thick brown oil, which was dissolved in acetonitrile (200 mL) and dried under vacuum. The residue was then dissolved in toluene (200 mL) and again dried under vacuum. The resulting crude 5-(3-bromo-propylidene)-5,11-dihydro-dibenzo[a,d]cyclohepten-10-one (6) was used without further purification in the next step. ESI MS m/z 327.0 (M+H)+. 1H NMR (d6-DMSO, 250 MHz): 7.98 (1H, d), 7.67-7.25 (7H, m), 5.76 (1H, t), 4.46 (1H, d), 3.73 (1H, d), 3.64 (2H, m), 2.83-2.50 (2H, m).

Workup

  1. customwas consumed
  2. additionThe mixture was diluted with H2O (100 mL)
  3. extractionthen extracted in a separatory funnel with ethyl ether (3×100 mL)
  4. washafter which the combined organic phases were washed with saturated sodium bicarbonate (3×50 mL)
  5. filtrationthe organic phase was filtered through a silica gel plug
  6. concentrationconcentrated under vacuum
  7. customto obtain a thick brown oil, which
  8. customdried under vacuum
  9. dissolutionThe residue was then dissolved in toluene (200 mL)
  10. customagain dried under vacuum
  11. customThe resulting crude 5-(3-bromo-propylidene)-5,11-dihydro-dibenzo[a,d]cyclohepten-10-one (6) was used without further purification in the next step

Sources & evidence

ORD record
ord-9d399cb31bb34792bc31b8247833ebd0
Source dataset
uspto-grants-2015_07
Patent number
US09090535B2

Reaction notes

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