Azobisisobutyronitrile → (4-bromo-5-methoxy-3-methyl-1-oxo-3,4-dihydro-1H-naphthalen-2-ylidene)-acetic acid ethyl ester

HRID 514036Notes

Reaction equation

HRID 514036 reaction equation
[CH2:1]([O:3][C:4](=[O:20])[CH:5]=[C:6]1[CH:15]([CH3:16])[CH2:14][C:13]2[C:8](=[CH:9][CH:10]=[CH:11][C:12]=2[O:17][CH3:18])[C:7]1=[O:19])[CH3:2].C1C(=O)N([Br:28])C(=O)C1.CC(N=NC(C#N)(C)C)(C#N)C>C(Cl)(Cl)(Cl)Cl>[CH2:1]([O:3][C:4](=[O:20])[CH:5]=[C:6]1[CH:15]([CH3:16])[CH:14]([Br:28])[C:13]2[C:8](=[CH:9][CH:10]=[CH:11][C:12]=2[O:17][CH3:18])[C:7]1=[O:19])[CH3:2]

Participants

5

Reactant 3

HCID 6547AzobisisobutyronitrileHCID 67184N-bromobutanimideHCID 86691539(5-methoxy-3-methyl-1-oxo-3,4-dihydro-1H-naphthalen-2-ylidene)-acetic acid ethyl ester

Product 1

HCID 86691540(4-bromo-5-methoxy-3-methyl-1-oxo-3,4-dihydro-1H-naphthalen-2-ylidene)-acetic acid ethyl esterYield 68%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

A mixture of (5-methoxy-3-methyl-1-oxo-3,4-dihydro-1H-naphthalen-2-ylidene)-acetic acid ethyl ester (480 mg), NBS (420 mg), and AIBN (30 mg) in CCl4 (18 mL) was refluxed for 3 hours. The reaction mixture was then cooled to room temperature, quenched with saturated sodium bicarbonate solution and extracted with dichloromethane (2×). The combined organics were washed with water, dried (Na2SO4), concentrated, and purified by flash column chromatography to give a light brown solid (420 mg) LCMS-ESI+ (m/z): [M+H]+ calcd for C16H18BrO4: 353.03. Found: 352.91.

Workup

  1. temperaturewas refluxed for 3 hours
  2. customquenched with saturated sodium bicarbonate solution
  3. extractionextracted with dichloromethane (2×)
  4. washThe combined organics were washed with water
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated
  7. custompurified by flash column chromatography

Sources & evidence

ORD record
ord-e120ede94d7d4c7f93322cd450bb149f
Source dataset
uspto-grants-2015_08
Patent number
US09102614B2

Reaction notes

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