Ethanol → HCID 86593888, compound

HRID 1269520Notes

Reaction equation

HRID 1269520 reaction equation
[N:1]1[CH:6]=[CH:5][CH:4]=[C:3]([C:7]2[CH:8]=[CH:9][C:10]([CH3:18])=[C:11]([CH:17]=2)[C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH:2]=1.[C:19]([OH:28])(=[O:27])[C@@H:20]([C@H:22]([C:24]([OH:26])=[O:25])[OH:23])[OH:21].C(O)C>C(O)(=O)C.[Pt]=O>[C:19]([OH:28])(=[O:27])[C@@H:20]([C@H:22]([C:24]([OH:26])=[O:25])[OH:23])[OH:21].[NH:1]1[CH2:6][CH2:5][CH2:4][C@@H:3]([C:7]2[CH:8]=[CH:9][C:10]([CH3:18])=[C:11]([CH:17]=2)[C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH2:2]1

Participants

6

Reactant 3

HCID 702EthanolHCID 444305L-Tartaric acidHCID 18448504HCID 18448504, compound

Product 1

HCID 86593888HCID 86593888, compoundYield 35%

Reagents, catalysts & solvents 2

HCID 82844Platinum oxide (PtO)CatalystHCID 176Acetic AcidSolvent

Procedure

A 500 mL hydrogenation vessel was charged with 2.0 g platinum(II)oxide and purged with nitrogen. Ethyl 5-(3-pyridyl)-2-methylbenzoate (19.57 g, 81.10 mmol) was added as a solution in 200 mL acetic acid. The suspension was hydrogenated at 45 psi for 18 h. The catalyst was filtered through celite and the filter plug was washed with 200 mL acetic acid. The filtrate was concentrated under reduced pressure. The resultant oil was taken up in 500 mL water and made basic with 5N aqueous sodium hydroxide. This basic layer was extracted with ethyl acetate (2×500 mL) and the extracts were combined and dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The resultant oil was taken up in 200 mL hot ethanol. L-(+)-tartaric acid (12.17 g, 81.1 mmol) was added into the ethanol solution and was allowed to stir at ambient temperature for 48 h, forming a white precipitate that was collected by filtration. The white solid was recrystallized from hot 5% H2O/ethanol (300 mL) and then from 350 mL hot 20% H2O/ethanol to yield 11.25 g (35%, 95.8% ee) of (S)-ethyl 5-(3-piperidinyl)-2-methylbenzoate-L-tartaric acid salt as a white solid. The mother liquors were combined and concentrated under reduced pressure. The resultant oil was taken up in 300 mL water and made basic with 5N aqueous sodium hydroxide. This basic layer was extracted with ethyl acetate (2×300 mL) and the extracts were combined and dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The resultant oil was taken up in 200 mL hot ethanol. D-(−)-tartaric acid (6.82 g, 45.4 mmol) was added into the ethanol solution and was allowed to stir at ambient temperature for 48 h, forming a white precipitate that was collected by filtration. The white solid was recrystallized from hot 5% H2O/ethanol (300 mL) and then from 350 mL hot 20% H2O/ethanol to yield 13.51 g (42%, 100% ee) of (R)-ethyl 5-(3-piperidinyl)-2-methylbenzoate-D-tartaric acid salt as a white solid.

Workup

  1. custompurged with nitrogen
  2. filtrationThe catalyst was filtered through celite
  3. washthe filter plug was washed with 200 mL acetic acid
  4. concentrationThe filtrate was concentrated under reduced pressure
  5. extractionThis basic layer was extracted with ethyl acetate (2×500 mL)
  6. dry with materialdried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customforming a white precipitate that
  10. filtrationwas collected by filtration
  11. customThe white solid was recrystallized from hot 5% H2O/ethanol (300 mL)

Sources & evidence

ORD record
ord-b1e73ee5a2cf4c6aa57448da384e6efd
Source dataset
uspto-grants-2007_04
Patent number
US07199243B2

Reaction notes

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