Hydrochloric Acid → HCID 69931466, compound

HRID 429448Notes

Reaction equation

HRID 429448 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].[C:7]([O:10][C:11]1[CH:16]=[CH:15][C:14]([C:17]2[C:26]3[C:21](=[CH:22][CH:23]=[C:24]([O:27][CH3:28])[CH:25]=3)[O:20][C:19](=O)[C:18]=2[C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)=[CH:13][CH:12]=1)(=O)[CH3:8].Cl.C(=O)([O-])[O-].[K+].[K+].Cl.ClCC[N:47]1[CH2:51][CH2:50][CH2:49][CH2:48]1.[I-].[Na+]>O1CCCC1.O.C(O)C.[Pd]>[CH3:28][O:27][C:24]1[CH:25]=[C:26]2[C:21](=[CH:22][CH:23]=1)[O:20][CH2:19][C@@H:18]([C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1)[C@H:17]2[C:14]1[CH:13]=[CH:12][C:11]([O:10][CH2:7][CH2:8][N:47]2[CH2:51][CH2:50][CH2:49][CH2:48]2)=[CH:16][CH:15]=1

Participants

11

Reactant 6

HCID 313Hydrochloric AcidHCID 5238Sodium IodideHCID 11430Potassium CarbonateHCID 816681-(2-Chloroethyl)pyrrolidine hydrochlorideHCID 18355594HCID 18355594, compoundHCID 21226445Aluminium lithium hydride

Product 1

HCID 69931466HCID 69931466, compound

Reagents, catalysts & solvents 4

HCID 23938PalladiumCatalystHCID 702EthanolSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
65 °C

Procedure

Lithium aluminium hydride (0.96 g, 2.54 mmol) was added in small portions to a stirred solution of 4-(4-acetoxyphenyl)-3-phenyl-6-methoxy-coumarin (0.49 g, 1.27 mmol) in tetrahydrofuran (75 ml). The resulting mixture was stirred for 30 min., 6M hydrochloric acid (4 ml) added dropwise, and the mixture heated to 65° C. for 3 h. The mixture was cooled to room temperature, diluted with 100 ml water, and the product extracted into ethyl acetate (2×100 ml). The extracts were washed with brine, dried over sodium sulfate and evaporated to give a yellow gum. This gum was dissolved in ethanol (100 ml), and palladium on carbon (5%, 0.045 g, 0.02 mmol) added, then the mixture was hydrogenated for 18 h. The catalyst was removed by filtration and the solvents evaporated to give an orange gum, which was vacuum dried. The gum was dissolved in dry acetone (20 ml) then potassium carbonate (1.87 g, 13.50 mmol), 1-(2-chloroethyl)pyrrolidine hydrochloride (0.257 g, 1.51 mmol) and sodium iodide (0.01 g, catalyst) were added and the mixture heated to 60° C. for 20 h. The inorganic solids were removed by filtration and the solvent removed to give an orange gum, which was purified by column chromatography on silica gel 60 with 9:1 dichloromethane/methanol eluent. This gave the product as a pale orange gum, which was vacuum dried.

Workup

  1. temperatureThe mixture was cooled to room temperature
  2. extractionthe product extracted into ethyl acetate (2×100 ml)
  3. washThe extracts were washed with brine
  4. dry with materialdried over sodium sulfate
  5. customevaporated
  6. customto give a yellow gum
  7. waitthe mixture was hydrogenated for 18 h
  8. customThe catalyst was removed by filtration
  9. customthe solvents evaporated
  10. customto give an orange gum, which
  11. customdried
  12. dissolutionThe gum was dissolved in dry acetone (20 ml)
  13. temperaturethe mixture heated to 60° C. for 20 h
  14. customThe inorganic solids were removed by filtration
  15. customthe solvent removed
  16. customto give an orange gum, which
  17. customwas purified by column chromatography on silica gel 60 with 9:1 dichloromethane/methanol eluent

Sources & evidence

ORD record
ord-fb74769504b0444e909a96a1bd9da23a
Source dataset
uspto-grants-2001_11
Patent number
US06316494B1

Reaction notes

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