Bromoacetonitrile → HCID 86658359, compound

HRID 931556Notes

Reaction equation

HRID 931556 reaction equation
[NH2:1][C:2]1([CH2:18][OH:19])[C:15]2[CH:14]=[C:13]([Cl:16])[N:12]=[CH:11][C:10]=2[O:9][C:8]2[C:3]1=[CH:4][C:5]([Br:17])=[CH:6][CH:7]=2.Br[CH2:21][C:22]#[N:23].[OH-].[Na+]>S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC.C1COCC1>[NH2:1][C:2]1([CH2:18][O:19][CH2:21][C:22]#[N:23])[C:15]2[CH:14]=[C:13]([Cl:16])[N:12]=[CH:11][C:10]=2[O:9][C:8]2[C:3]1=[CH:4][C:5]([Br:17])=[CH:6][CH:7]=2

Participants

6

Reactant 3

HCID 11534BromoacetonitrileHCID 14798Sodium HydroxideHCID 58465926HCID 58465926, compound

Product 1

HCID 86658359HCID 86658359, compound

Reagents, catalysts & solvents 2

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 8028TetrahydrofuranSolvent

Procedure

A 4-neck 3000-mL RBF with a mechanical stirrer was charged with (5-amino-7-bromo-3-chloro-5H-chromeno[2,3-c]pyridin-5-yl)methanol (29.43 g, 86 mmol), tetrabutylammonium hydrogen sulfate (5.85 g, 17.23 mmol), THF (431 mL), and bromoacetonitrile (30.0 mL, 431 mmol) to give a clear, brown solution. The resulting solution was stirred vigorously for 5 min, then a 2N aq. solution of NaOH (431 mL, 862 mmol) was added in one portion. The mixture was stirred overnight and concentrated under vacuum. The remaining material was partitioned between EtOAc (500 mL) and water (500 mL). The layers were separated and the aqueous layer was extracted with EtOAc (2×250 mL). The combined organic layers were washed with brine and dried over magnesium sulfate. The solvent was removed under reduced pressure. The residue was taken up in DCM and filtered through a short pad of silica gel. The filtrate was concentrated and purified by silica gel chromatography (0.5% MeOH/DCM) to provide 2-((5-amino-7-bromo-3-chloro-5H-chromeno[2,3-c]pyridin-5-yl)methoxy)acetonitrile.

Workup

  1. customto give a clear, brown solution
  2. stirringThe mixture was stirred overnight
  3. concentrationconcentrated under vacuum
  4. customThe remaining material was partitioned between EtOAc (500 mL) and water (500 mL)
  5. customThe layers were separated
  6. extractionthe aqueous layer was extracted with EtOAc (2×250 mL)
  7. washThe combined organic layers were washed with brine
  8. dry with materialdried over magnesium sulfate
  9. customThe solvent was removed under reduced pressure
  10. filtrationfiltered through a short pad of silica gel
  11. concentrationThe filtrate was concentrated
  12. custompurified by silica gel chromatography (0.5% MeOH/DCM)

Sources & evidence

ORD record
ord-83e234d1fec74a388278197dc680dbd6
Source dataset
uspto-grants-2016_03
Patent number
US09296759B2

Reaction notes

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