Diethyl Ether → 6-Bromo-2,3-dihydro-5-nitro-1H-inden-1-one

HRID 1267809Notes

Reaction equation

HRID 1267809 reaction equation
N[C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][C:10]=1[Br:11])[C:7](=[O:12])[CH2:6][CH2:5]2.[N:13]([O-:15])=[O:14].[Na+].C(OCC)C>F[B-](F)(F)F.[H+].O.[Cu]>[N+:13]([C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][C:10]=1[Br:11])[C:7](=[O:12])[CH2:6][CH2:5]2)([O-:15])=[O:14]

Participants

7

Reactant 3

HCID 3283Diethyl EtherHCID 103987765-Amino-6-bromo-2,3-dihydro-1H-inden-1-oneHCID 23668193Sodium Nitrite2×

Product 1

HCID 100609406-Bromo-2,3-dihydro-5-nitro-1H-inden-1-oneYield 52.6%

Reagents, catalysts & solvents 3

HCID 23978CopperCatalystHCID 962WaterSolventHCID 28118Tetrafluoroboric acidSolvent

Procedure

To a suspension of 5-amino-6-bromo-1-indanone (30.0 g, 0.13 mol) in 20% aqueous fluoroboric acid (120 mL) at 0° C. was added dropwise 4M aqueous NaNO2 (50 mL, 0.20 mol) over a period of 30 min. The mixture was stirred for 30 min after completion of addition. The resulting foamy suspension was added portionwise to a vigorously stirred mixture of copper powder (40 g, 0.62 mol) and sodium nitrite (120 g, 1.74 mol) in water (240 mL) at room temperature over a period of 15 min. During the addition, excessive foaming was broken up by the addition of small amounts of diethyl ether. After further stirring for 30 min, the mixture was filtered through celite, washed with ethyl acetate (5′300 mL). The ethyl acetate layer was separated, washed with brine, dried over anhydrous MgSO4 and concentrated in vacuo. Chromatography over silica gel, eluting with CH2Cl2, yielded 17.5 g (51%) of the title compound as a pale yellow solid.

Workup

  1. additionafter completion of addition
  2. additionDuring the addition, excessive foaming
  3. stirringAfter further stirring for 30 min
  4. filtrationthe mixture was filtered through celite
  5. washwashed with ethyl acetate (5′300 mL)
  6. customThe ethyl acetate layer was separated
  7. washwashed with brine
  8. dry with materialdried over anhydrous MgSO4
  9. concentrationconcentrated in vacuo
  10. washChromatography over silica gel, eluting with CH2Cl2

Sources & evidence

ORD record
ord-3618d49ad8014ee685235c43706383c6
Source dataset
uspto-grants-2003_04
Patent number
USRE038103E1

Reaction notes

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