Dichloromethane → HCID 58382176, compound

HRID 1628031Notes

Reaction equation

HRID 1628031 reaction equation
[H-].[Na+].[Br:3][C:4]1[C:12]2[C:7](=[N:8][CH:9]=[C:10]([CH2:13][NH:14][C:15](=[O:21])[O:16][C:17]([CH3:20])([CH3:19])[CH3:18])[N:11]=2)[NH:6][CH:5]=1.[S:22](Cl)([C:25]1[CH:31]=[CH:30][C:28]([CH3:29])=[CH:27][CH:26]=1)(=[O:24])=[O:23].C(Cl)Cl>CN(C=O)C.O>[Br:3][C:4]1[C:12]2[C:7](=[N:8][CH:9]=[C:10]([CH2:13][NH:14][C:15](=[O:21])[O:16][C:17]([CH3:18])([CH3:20])[CH3:19])[N:11]=2)[N:6]([S:22]([C:25]2[CH:31]=[CH:30][C:28]([CH3:29])=[CH:27][CH:26]=2)(=[O:24])=[O:23])[CH:5]=1

Participants

7

Reactant 4

HCID 6344DichloromethaneHCID 73974-Toluenesulfonyl chlorideHCID 24758Sodium hydrideHCID 58381981HCID 58381981, compound

Product 1

HCID 58382176HCID 58382176, compoundYield 101.8%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent3×

Conditions

Temperature
0 °C

Procedure

A flask was charged with NaH (60 wt % in mineral oil, 0.025 g, 0.64 mmol) in DMF (2.0 mL). The suspension was cooled to about 0° C., followed by the addition of a solution of tert-butyl (7-bromo-5H-pyrrolo[2,3-b]pyrazin-2-yl)methylcarbamate (0.16 g, 0.49 mmol) in DMF (2.0 mL). The mixture was stirred at about 0° C. for about 10 min and then at rt for about 20 min. The mixture was cooled to about 0° C. followed by the addition of a solution of TsCl (0.112 g, 0.587 mmol) in DMF (1.0 mL). The mixture was stirred at 0° C. for about 20 min and warmed to rt and stirred for about 1 h. To the mixture were added DCM (10 mL) and water (10 mL). The organic layer was isolated and dried over anhydrous MgSO4, filtered and concentrated under reduced pressure. EtOAc (10 mL) and heptane (10 mL) were added and then the mixture was concentrated under reduced pressure to give tert-butyl (7-bromo-5-tosyl-5H-pyrrolo[2,3-b]pyrazin-2-yl)methylcarbamate (0.24 g, 91%): LC/MS (Table 2, Method c) Rf=1.59 min; MS m/z 481 (M+H)+.

Workup

  1. waitat rt for about 20 min
  2. temperatureThe mixture was cooled to about 0° C.
  3. stirringThe mixture was stirred at 0° C. for about 20 min
  4. temperaturewarmed to rt
  5. stirringstirred for about 1 h
  6. customThe organic layer was isolated
  7. dry with materialdried over anhydrous MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. additionEtOAc (10 mL) and heptane (10 mL) were added
  11. concentrationthe mixture was concentrated under reduced pressure

Sources & evidence

ORD record
ord-6d5e812cd77d4e0c95f3223f3227f8ed
Source dataset
uspto-grants-2014_07
Patent number
US08785639B2

Reaction notes

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