Potassium Fluoride → 2-Amino-3-nitro-5-propenyl-benzoic acid methyl ester

HRID 1845044Notes

Reaction equation

HRID 1845044 reaction equation
[CH3:1][O:2][C:3](=[O:15])[C:4]1[CH:9]=[C:8](Br)[CH:7]=[C:6]([N+:11]([O-:13])=[O:12])[C:5]=1[NH2:14].[CH2:16]([Sn](CCCC)(CCCC)C=CC)[CH2:17][CH2:18]C.[F-].[K+]>O1CCOCC1>[CH3:1][O:2][C:3](=[O:15])[C:4]1[CH:9]=[C:8]([CH:16]=[CH:17][CH3:18])[CH:7]=[C:6]([N+:11]([O-:13])=[O:12])[C:5]=1[NH2:14]

Participants

5

Reactant 3

HCID 522689Potassium FluorideHCID 17984898Methyl 2-amino-5-bromo-3-nitrobenzoateHCID 57369809Stannane, tributyl-1-propenyl-

Product 1

HCID 669404292-Amino-3-nitro-5-propenyl-benzoic acid methyl esterYield 77%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

A solution of 0.5 g (1.8 mmol) of the above ester 0.9 g (2.7 mmol) of tributyl-propenyl-stannane, 0.18 g (0.18 mmol mmol) of (tetrakistriphenyl phosphine) palladium (0) in 25 mL of dioxane was degassed with nitrogen for 20 min then refluxed under nitrogen for 12 h. The reaction mixture was cooled, 20 mL of 2 M KF solution was added. The mixture was stirred for 20 min, extracted with ethyl acetate washed with water and brine. The residue was purified by column chromatography using 8:2 hexane and ethyl acetate to afford 0.35 g (77%) of the 2-amino-3-nitro-5-propenyl-benzoic acid methyl ester as a solid LCMS: 239 (M+1)+.

Workup

  1. temperaturethen refluxed under nitrogen for 12 h
  2. temperatureThe reaction mixture was cooled
  3. extractionextracted with ethyl acetate
  4. washwashed with water and brine
  5. customThe residue was purified by column chromatography

Sources & evidence

ORD record
ord-6bdfe0f4dab243589d51e38ebbb67b16
Source dataset
uspto-grants-2015_02
Patent number
US08946259B2

Reaction notes

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