Triethylamine → (+)-Ethyl 2-[[[5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-3H-imidazo[4,5-b]pyridin-3-yl]carbonyl](methyl)amino]ethyl carbonate

HRID 1022348Notes

Reaction equation

HRID 1022348 reaction equation
[CH3:1][O:2][C:3]1[N:8]=[C:7]2[N:9]=[C:10]([S:12]([CH2:14][C:15]3[C:20]([CH3:21])=[C:19]([O:22][CH3:23])[C:18]([CH3:24])=[CH:17][N:16]=3)=[O:13])[NH:11][C:6]2=[CH:5][CH:4]=1.[C:25](=[O:37])([O:34][CH2:35][CH3:36])[O:26][CH2:27][CH2:28][N:29]([C:31](Cl)=[O:32])[CH3:30].C(N(CC)CC)C>O1CCCC1.CN(C)C1C=CN=CC=1>[C:25](=[O:37])([O:26][CH2:27][CH2:28][N:29]([C:31]([N:9]1[C:7]2=[N:8][C:3]([O:2][CH3:1])=[CH:4][CH:5]=[C:6]2[N:11]=[C:10]1[S:12]([CH2:14][C:15]1[C:20]([CH3:21])=[C:19]([O:22][CH3:23])[C:18]([CH3:24])=[CH:17][N:16]=1)=[O:13])=[O:32])[CH3:30])[O:34][CH2:35][CH3:36]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 636411TenatoprazoleHCID 116081722-[(Chlorocarbonyl)(methyl)amino]ethyl ethyl carbonate

Product 1

HCID 10029626(+)-Ethyl 2-[[[5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-3H-imidazo[4,5-b]pyridin-3-yl]carbonyl](methyl)amino]ethyl carbonate

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
50 °C

Procedure

5-Methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-imidazo[4,5-b]pyridine synthesized according to the method described in JP-A-63-146882 was subjected to preparative HPLC for optical resolution to give a (−) enantiomeric form (0.10 g) thereof. To a solution (5 mL) of this form in tetrahydrofuran were added 2-[(chlorocarbonyl)(methyl)amino]ethyl ethyl carbonate (0.081 g) obtained in Reference Example 34, triethylamine (0.080 mL) and 4-dimethylaminopyridine (0.007 g) and the mixture was stirred at 50° C. for 18 hrs. After concentration under reduced pressure, water (30 mL) was added to the residue and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (30 mL) and dried over anhydrous sodium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=2:1) to give the title compound (0.053 g) as a colorless oil.

Workup

  1. customto give a (−) enantiomeric form (0.10 g)
  2. concentrationAfter concentration under reduced pressure, water (30 mL)
  3. additionwas added to the residue
  4. extractionthe mixture was extracted with ethyl acetate (50 mL)
  5. washThe ethyl acetate layer was washed with saturated brine (30 mL)
  6. dry with materialdried over anhydrous sodium sulfate
  7. concentrationAfter concentration under reduced pressure
  8. customthe residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=2:1)

Sources & evidence

ORD record
ord-b8a32857f2834ceda08ae441029f71a6
Source dataset
uspto-grants-2014_05
Patent number
US08722084B2

Reaction notes

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