Ammonium Chloride → HCID 22020919, compound

HRID 1793330Notes

Reaction equation

HRID 1793330 reaction equation
Br[CH:2]([CH2:19][Br:20])[CH2:3][O:4][C:5]1[CH:6]=[N:7][CH:8]=[CH:9][C:10]=1[O:11]CC1C=CC=CC=1.[NH4+].[Cl-].C(C(C(C([O-])=O)O)O)([O-])=O.[Na+].[K+]>C(Cl)Cl>[Br:20][CH2:19][CH:2]1[CH2:3][O:4][C:5]2[CH:6]=[N:7][CH:8]=[CH:9][C:10]=2[O:11]1

Participants

5

Reactant 3

HCID 25517Ammonium ChlorideHCID 9855836Potassium sodium tartarateHCID 22020935HCID 22020935, compound

Product 1

HCID 22020919HCID 22020919, compoundYield 13.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of intermediate (46) (0.0166 mol) in DCM (270 ml), FeCl3 (0.033 mol) was added portionwise and the mixture was stirred at room temperature overnight. The reaction mixture was treated with a saturated NH4Cl-solution and with a diluted solution of potassium sodium tartrate and then it was filtered off over celite. The solvent was evaporated until dry and the residue was treated with methanol and then filtered off. The filtrate was evaporated until dry and the residue was treated with 2,3-dihydroxy butaenedioic acid, monopotassium monosodium salt (1 g) in ethanol and refluxed for 18 hours. The cooled reaction mixture was filtered off over celite and the filtrate was evaporated until dry. The residue was washed with water and extracted with DCM. The separated organic layer was dried, filtered and the solvent was evaporated until dry. The residue was purified by flash column chromatography over silica gel (eluent: ethyl acetate/(MeOH/NH3) 96/4). The product fractions were collected and the solvent was evaporated, yielding 0.52 g of 2-(bromomethyl)-2,3-dihydro-[1,4]dioxino-[2,3-c]pyridine (intermediate 47).

Workup

  1. filtrationit was filtered off over celite
  2. customThe solvent was evaporated
  3. customuntil dry
  4. additionthe residue was treated with methanol
  5. filtrationfiltered off
  6. customThe filtrate was evaporated
  7. customuntil dry
  8. additionthe residue was treated with 2,3-dihydroxy butaenedioic acid, monopotassium monosodium salt (1 g) in ethanol
  9. temperaturerefluxed for 18 hours
  10. customThe cooled reaction mixture
  11. filtrationwas filtered off over celite
  12. customthe filtrate was evaporated
  13. customuntil dry
  14. washThe residue was washed with water
  15. extractionextracted with DCM
  16. customThe separated organic layer was dried
  17. filtrationfiltered
  18. customthe solvent was evaporated
  19. customuntil dry
  20. customThe residue was purified by flash column chromatography over silica gel (eluent: ethyl acetate/(MeOH/NH3) 96/4)
  21. customThe product fractions were collected
  22. customthe solvent was evaporated

Sources & evidence

ORD record
ord-94d8148633e341e8970b0d1286e9d02e
Source dataset
uspto-grants-2006_07
Patent number
US07081453B2

Reaction notes

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