Bromine → HCID 68863959, compound

HRID 1725950Notes

Reaction equation

HRID 1725950 reaction equation
[CH3:1][C:2]1([CH3:16])[CH2:11][CH2:10][C:9]2[C:4](=[CH:5][C:6]([N+:12]([O-])=O)=[CH:7][CH:8]=2)[C:3]1=[O:15].[Cl-].[NH4+].[Br:19]Br.C(=O)([O-])O.[Na+]>C(Cl)(Cl)Cl.CN(C)C=O.C(OCC)(=O)C.[Fe].C(O)C.O>[NH2:12][C:6]1[C:5]([Br:19])=[C:4]2[C:9]([CH2:10][CH2:11][C:2]([CH3:16])([CH3:1])[C:3]2=[O:15])=[CH:8][CH:7]=1

Participants

10

Reactant 4

HCID 24408BromineHCID 25517Ammonium ChlorideHCID 516892Sodium BicarbonateHCID 11775597HCID 11775597, compound

Product 1

HCID 68863959HCID 68863959, compoundYield 56.8%

Reagents, catalysts & solvents 5

HCID 23925IronCatalystHCID 6212ChloroformSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolventHCID 19096565Water ethanolSolvent

Procedure

A mixture of Example 362A (1.05 g, 4.79 mmol) in 4:1 ethanol/water (20 mL) was reduced with iron (1.1 g) in the presence of ammonium chloride (0.12 g) using the procedure described in Example 275A. The crude product (0.91 g, 4.79 mmol) was treated with bromine (0.245 mL, 4.79 mmol) in 9 mL of chloroform and 0.9 mL of N,N-dimethylformamide following the procedure described in Example 275B. The obtained hydrobromide salt was treated with 10% sodium hydrogen carbonate in ethyl acetate. The ethyl acetate layer was washed with brine (4×), dried (Na2SO4), filtered, and concentrated. The residue was purified by silica gel column chromatography eluting with 10% ethyl acetate in n-hexane to provide 730 mg of the desired product. MS (ESI(−)) m/e 266 (M−H)−; 1H NMR (300 MHz, DMSO-d6) δ 6.97 (m, 2H), 5.39 (m, 2H), 2.80 (t, 2H), 1.84 (t, 2H), 1.10 (s, 6H).

Workup

  1. washThe ethyl acetate layer was washed with brine (4×)
  2. dry with materialdried (Na2SO4)
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe residue was purified by silica gel column chromatography
  6. washeluting with 10% ethyl acetate in n-hexane

Sources & evidence

ORD record
ord-d449e10a71ba4b23af8091f1ba497703
Source dataset
uspto-grants-2009_02
Patent number
US07491718B2

Reaction notes

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