Bromine → HCID 22020941, compound

HRID 1793327Notes

Reaction equation

HRID 1793327 reaction equation
[O:1]1[C:10]2[C:5](=[N:6][CH:7]=[CH:8][CH:9]=2)[O:4][C@@H:3]([CH2:11][OH:12])[CH2:2]1.[Br:13]Br.[O-]S([O-])=O.[Na+].[Na+]>C(Cl)Cl.C([O-])([O-])=O.[Na+].[Na+]>[Br:13][C:8]1[CH:9]=[C:10]2[O:1][CH2:2][C@H:3]([CH2:11][OH:12])[O:4][C:5]2=[N:6][CH:7]=1.[Br:13][C:9]1[CH:8]=[CH:7][N:6]=[C:5]2[O:4][CH:3]([CH2:11][OH:12])[CH2:2][O:1][C:10]=12

Participants

7

Reactant 3

HCID 24408BromineHCID 24437Sodium SulfiteHCID 69255535HCID 69255535, compound

Product 2

HCID 22020941HCID 22020941, compoundHCID 69255905HCID 69255905, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 10340Sodium CarbonateSolvent2×

Procedure

To a solution of intermediate (2-a) (0.03 mol) in DCM (50 ml) and Na2CO3 saturated (50 ml), bromine (0.09 mol) was added dropwise and the reaction mixture was stirred for 16 hours at room temperature. Then a Na2SO3-solution (10%) was added and the mixture was stirred for 5 minutes at room temperature and then neutralized with a saturated Na2CO3-solution. The aqueous layer was extracted with DCM and the separated combined organic layers were dried, filtered and the solvent was evaporated. The residue was purified by short open column chromatography over silica gel (eluent: CH2Cl2/(MeOH/NH3 saturated) 95/5). The desired fractions were collected and the solvent was evaporated. The residue was purified by high-performance liquid chromatography over silica gel (eluent: CH2Cl2/(MeOH/NH3 saturated) 97/3). The product fractions were collected and the solvent was evaporated, yielding 2.7 g of (S)-7-bromo-2,3-dihydro-[1,4]dioxino[2,3-b]pyridine-3-methanol (intermediate 41) and 0.26 g of 8-bromo-2,3-dihydro-[1,4]dioxino[2,3-b]pyridine-3-methanol (intermediate 42)

Workup

  1. stirringthe mixture was stirred for 5 minutes at room temperature
  2. extractionThe aqueous layer was extracted with DCM
  3. customwere dried
  4. filtrationfiltered
  5. customthe solvent was evaporated
  6. customThe residue was purified by short open column chromatography over silica gel (eluent: CH2Cl2/(MeOH/NH3 saturated) 95/5)
  7. customThe desired fractions were collected
  8. customthe solvent was evaporated
  9. customThe residue was purified by high-performance liquid chromatography over silica gel (eluent: CH2Cl2/(MeOH/NH3 saturated) 97/3)
  10. customThe product fractions were collected
  11. customthe solvent was evaporated

Sources & evidence

ORD record
ord-c3d23e65adee4b12b12b3b4c3cb07888
Source dataset
uspto-grants-2006_07
Patent number
US07081453B2

Reaction notes

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