2-[(Chlorocarbonyl)(methyl)amino]ethyl ethyl carbonate → (+)-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 2096085Notes

Reaction equation

HRID 2096085 reaction equation
[C:1](=[O:13])([O:10][CH2:11][CH3:12])[O:2][CH2:3][CH2:4][N:5]([C:7](Cl)=[O:8])[CH3:6].C(=O)(OCCN(C([N:25]1[C:33]2[C:28](=[N:29][C:30]([O:34][CH3:35])=[CH:31][CH:32]=2)[N:27]=[C:26]1[S:36]([CH2:38][C:39]1[C:44]([CH3:45])=[C:43]([O:46][CH3:47])[C:42]([CH3:48])=[CH:41][N:40]=1)=[O:37])=O)C)OCC>CN(C)C1C=CN=CC=1.C(N(CC)CC)C>[C:1](=[O:13])([O:2][CH2:3][CH2:4][N:5]([C:7]([N:27]1[C:28]2=[N:29][C:30]([O:34][CH3:35])=[CH:31][CH:32]=[C:33]2[N:25]=[C:26]1[S:36]([CH2:38][C:39]1[C:44]([CH3:45])=[C:43]([O:46][CH3:47])[C:42]([CH3:48])=[CH:41][N:40]=1)=[O:37])=[O:8])[CH3:6])[O:10][CH2:11][CH3:12]

Participants

5

Reactant 2

HCID 116081722-[(Chlorocarbonyl)(methyl)amino]ethyl ethyl carbonateHCID 86606461HCID 86606461, compound

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 8471TriethylamineSolvent

Conditions

Temperature
50 °C

Procedure

To a solution of (+)-enantiomer (0.10 g) in tetrahydrofuran (5 mL), which was obtained by optically resolving 5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-imidazo[4,5-b]pyridine synthesized by a method described in JP-A 63-146882 with preparative HPLC, were added 2-[(chlorocarbonyl)(methyl)amino]ethyl ethyl carbonate (0.081 g) obtained in Reference Synthetic Example 34, triethylamine (0.080 mL) and 4-dimethylaminopyridine (0.007 g), and stirred at 50° C. for 18 hrs. The reaction solution was concentrated under reduced pressure, and to the residue was added water (30 mL), and extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (30 mL), and dried over anhydrous sodium sulfate. After concentrating under reduced pressure, the residue was purified with basic silica gel column chromatography (eluted with ethyl acetate:hexane=2:1) to give a mixture of 2:1 of title compound and (+)-ethyl 2-[[[5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-imidazo[4,5-b]pyridin-1-yl]carbonyl](methyl)amino]ethyl carbonate as colorless oil (0.115 g).

Workup

  1. customsynthesized by a method
  2. concentrationThe reaction solution was concentrated under reduced pressure
  3. additionto the residue was added water (30 mL)
  4. extractionextracted 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 concentrating under reduced pressure
  8. customthe residue was purified with basic silica gel column chromatography (eluted with ethyl acetate:hexane=2:1)
  9. customto give

Sources & evidence

ORD record
ord-e78ddd61065f42e2b28b0337ff830a60
Source dataset
uspto-grants-2013_05
Patent number
US08449911B2

Reaction notes

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