Trifluoroacetic acid → HCID 23138722, compound

HRID 1171753Notes

Reaction equation

HRID 1171753 reaction equation
C([O-])(=S)C.[K+].[C:6]([S:9][CH:10]1[CH2:15][CH2:14][N:13](C(C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[CH2:12]/[C:11]/1=[CH:35]\[C:36]1[CH:37]=[N:38][N:39]([CH2:41][C:42]([O:44][CH2:45][CH3:46])=[O:43])[CH:40]=1)(=[O:8])[CH3:7].C(SC(C1C=NN(CC(OCC)=O)C=1)C1CN(C(C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)CCC=1)(=O)C.[F:88][C:89]([F:94])([F:93])[C:90]([OH:92])=[O:91]>CS(C)=O.O.ClCCl>[F:88][C:89]([F:94])([F:93])[C:90]([OH:92])=[O:91].[C:6]([S:9][CH:10]1[CH2:15][CH2:14][NH:13][CH2:12]/[C:11]/1=[CH:35]\[C:36]1[CH:37]=[N:38][N:39]([CH2:41][C:42]([O:44][CH2:45][CH3:46])=[O:43])[CH:40]=1)(=[O:8])[CH3:7]

Participants

8

Reactant 4

HCID 6422Trifluoroacetic acidHCID 23139071HCID 23139071, compoundHCID 23139100HCID 23139100, compoundHCID 23670855Potassium ethanethioate

Product 1

HCID 23138722HCID 23138722, compoundYield 33%

Reagents, catalysts & solvents 3

HCID 679Dimethyl SulfoxideSolventHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of the mixture as above in dimethyl sulfoxide (100 ml), was added potassium thioacetate (12.3 g). The resulting mixture was stirred at 80° C. for 15 hours, cooled to room temperature, and diluted with water to stop the reaction. The products were extracted with ethyl acetate. The organic layer was washed with a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous aqueous sodium chloride, and solvents were evaporated in vacuo. The residue was purified by chromatography on silica gel using a mixture of hexane, ethyl acetate and dichloromethane (2:1:1) as the eluent to afford an approximately 7:6:1 mixture of (E)-4-(acetylsulfanyl)-3-{[1-(ethoxycarbonylmethyl)-1H-pyrazol-4-yl]methylidene}-1-(triphenylmethyl)piperidine, its (Z)-isomer and 5-{(acetylsulfanyl)[1-(ethoxycarbonylmethyl)-1H-pyrazol-4-yl]methyl}-1-(triphenylmethyl)-1,2,3,6-tetrahydropyridine (5.52 g). To a solution of the above mixture in dichloromethane (300 ml) was added trifluoroacetic acid (1.9 ml). The resulting mixture was stirred at room temperature for 15 minutes. The solvent was evaporated in vacuo, and the residue was purified by chromatography on silica gel using a mixture of dichloromethane and methanol (10:1) as the eluent to afford the title compound as a yellow amorphous solid (1.75 g, overall yield: 33%).

Workup

  1. temperaturecooled to room temperature
  2. customthe reaction
  3. extractionThe products were extracted with ethyl acetate
  4. washThe organic layer was washed with a saturated aqueous sodium chloride solution
  5. dry with materialThe organic layer was dried over anhydrous aqueous sodium chloride, and solvents
  6. customwere evaporated in vacuo
  7. customThe residue was purified by chromatography on silica gel using
  8. additiona mixture of hexane, ethyl acetate and dichloromethane (2:1:1) as the eluent
  9. customto afford
  10. stirringThe resulting mixture was stirred at room temperature for 15 minutes
  11. customThe solvent was evaporated in vacuo
  12. customthe residue was purified by chromatography on silica gel using
  13. additiona mixture of dichloromethane and methanol (10:1) as the eluent

Sources & evidence

ORD record
ord-a609d52ea436482b8361467fc9251384
Source dataset
uspto-grants-2010_11
Patent number
US07829580B2

Reaction notes

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