HCID 22485789, compound → HCID 17937453, compound

HRID 2181266Notes

Reaction equation

HRID 2181266 reaction equation
C([Si](C1C=CC=CC=1)(C1C=CC=CC=1)[O:6][C:7]1[CH:8]=[C:9]([C:13]2[CH:18]([CH2:19][N:20]([CH3:22])[CH3:21])[CH2:17][CH2:16][C:15](=[O:23])[CH:14]=2)[CH:10]=[CH:11][CH:12]=1)(C)(C)C>CO.[Pd]>[CH3:22][N:20]([CH2:19][CH:18]1[CH2:17][CH2:16][C:15](=[O:23])[CH2:14][CH:13]1[C:9]1[CH:10]=[CH:11][CH:12]=[C:7]([OH:6])[CH:8]=1)[CH3:21]

Participants

4

Reactant 1

HCID 22485789HCID 22485789, compound

Product 1

HCID 17937453HCID 17937453, compoundYield 39.1%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

25 g 3-[3-(tert-butyl-diphenyl-silanyloxy)-phenyl]-4-dimethylaminomethyl-cyclohex-2-enone were dissolved in 110 ml absolute methanol. 2,8 g palladium-on-charcoal (10%) were added as a catalyst, while stirring and passing dry nitrogen over. Hydrogenation was then carried out for five hours under a pressure of 0.2 bar and at a temperature of 20° C. After filtration the solvent was evaporated off in vacuo and the residue was dissolved in 60 ml tetrahydrofuran. 15 ml tetrabutylammonium fluoride were then added at room temperature. When the reaction had ended the mixture was quenched with water and then extracted with ethyl acetate. The organic phase was washed with saturated sodium chloride solution. The organic phase was then dried over magnesium sulfate and the solvent was evaporated in vacuo. The residue was purified by column chromatography on silica gel with ethyl acetate/methanol/diisopropyl ether=4/1/5 as the eluting agent. 5 g rac-cis-[4-dimethylaminomethyl-3-(3-hydroxy-phenyl)-cyclohexanone in the form of an oil were obtained as the first product fraction. To prepare the hydrochloride, the base was dissolved in acetone, and an equimolar amount of water and trimethylchlorosilane was added. The hydrochloride which had precipitated out was filtered off with suction and dried in vacuo. 4.8 g (32.9% of theory) rac-cis-[4-dimethylaminomethyl-3-(3-hydroxy-phenyl)-cyclohexanone hydrochloride were obtained in this way. The second product fraction gave 3.5 g rac-trans-[4-dimethylaminomethyl-3-(3-hydroxy-phenyl)-cyclohexanone, likewise as an oil. To prepare the hydrochloride, the base was dissolved in acetone, and an equimolar amount of water and trimethylchlorosilane was added. The hydrochloride which had precipitated out was filtered off with suction and dried in vacuo. 3.2 g (21.9% of theory) rac-trans-[4-dimethylaminomethyl-3-(3-hydroxy-phenyl)-cyclohexanone hydrochloride were obtained in this way.

Workup

  1. filtrationAfter filtration the solvent
  2. customwas evaporated off in vacuo
  3. dissolutionthe residue was dissolved in 60 ml tetrahydrofuran
  4. addition15 ml tetrabutylammonium fluoride were then added at room temperature
  5. customwas quenched with water
  6. extractionextracted with ethyl acetate
  7. washThe organic phase was washed with saturated sodium chloride solution
  8. dry with materialThe organic phase was then dried over magnesium sulfate
  9. customthe solvent was evaporated in vacuo
  10. customThe residue was purified by column chromatography on silica gel with ethyl acetate/methanol/diisopropyl ether=4/1/5 as the eluting agent

Sources & evidence

ORD record
ord-0573b3130b5f4a65b2d0d0ee98870012
Source dataset
uspto-grants-2005_05
Patent number
US06890959B2

Reaction notes

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