Toluene → HCID 69557602, compound

HRID 2213025Notes

Reaction equation

HRID 2213025 reaction equation
[BH4-].[Li+].[CH3:3][C:4](=[CH2:24])[CH2:5][C:6]1([C:19](OCC)=[O:20])[CH2:11][CH2:10][N:9]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[CH2:8][CH2:7]1.C1(C)C=CC=CC=1.[Cl-].[NH4+]>O1CCCC1.O>[OH:20][CH2:19][C:6]1([CH2:5][C:4]([CH3:24])=[CH2:3])[CH2:11][CH2:10][N:9]([C:12]([O:14][C:15]([CH3:16])([CH3:17])[CH3:18])=[O:13])[CH2:8][CH2:7]1

Participants

7

Reactant 4

HCID 1140TolueneHCID 25517Ammonium ChlorideHCID 4148881Lithium borohydride2×HCID 69559116HCID 69559116, compound

Product 1

HCID 69557602HCID 69557602, compoundYield 67.2%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

Lithium borohydride (0.44 g, 20 mmol) was added to a solution of 1-(1,1-dimethylethyl) 4-ethyl 4-(2-methyl-2-propenyl)-1,4-piperidinedicarboxylate (Description 89, 3.11 g, 10 mmol) in tetrahydrofuran and the mixture was stirred under reflux for 18 hours. The mixture was cooled, toluene (20 mL) and lithium borohydride (0.44 g, 20 mmol) were added and the mixture was stirred under reflux for 6 hours. The mixture was cooled and saturated aqueous ammonium chloride (20 mL) and water (50 mL) were added. The mixture was extracted with ethyl acetate (3×500 mL) and the combined organic fractions were washed with aqueous citric acid (10%, 50 mL), saturated aqueous sodium hydrogen carbonate (50 mL) and brine (50 mL), dried (MgSO4) and the solvent was evaporated under reduced pressure. The residue was purified by flash column chromatography on silica gel, eluting with isohexane/EtOAc (70:30) to give the title compound as a colorless foam (1.81 g, 67%). 1H NMR (400 MHz, CDCl3) shows two slowly equilibrating tautomers; major: δ 4.92 (1H, s), 4.77 (1H, s), 3.86–3.20 (10H, m), 2.14 (2H, s), 1.82 (3H, s), and 1.46 (9H, s); minor; δ 4.87 (1H, s), 4.66 (1H, s), 3.86–3.20 (10H, m), 2.11 (2H, s), 1.76 (3H, s), and 1.46 (9H, s). m/z (ES+) 270 (M+1).

Workup

  1. temperatureunder reflux for 18 hours
  2. temperatureThe mixture was cooled
  3. stirringthe mixture was stirred
  4. temperatureunder reflux for 6 hours
  5. temperatureThe mixture was cooled
  6. extractionThe mixture was extracted with ethyl acetate (3×500 mL)
  7. washthe combined organic fractions were washed with aqueous citric acid (10%, 50 mL), saturated aqueous sodium hydrogen carbonate (50 mL) and brine (50 mL)
  8. dry with materialdried (MgSO4)
  9. customthe solvent was evaporated under reduced pressure
  10. customThe residue was purified by flash column chromatography on silica gel
  11. washeluting with isohexane/EtOAc (70:30)

Sources & evidence

ORD record
ord-a286253cda844795bd5cd6f3fbf9b0bd
Source dataset
uspto-grants-2006_09
Patent number
US07105507B2

Reaction notes

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