Water → 3-Isopropenyl-4-methoxy-5-nitrobenzonitrile

HRID 2093613Notes

Reaction equation

HRID 2093613 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:7]=[C:8]([N+:12]([O-:14])=[O:13])[C:9]=1[O:10][CH3:11])[C:5]#[N:6].O.[C:16](B(O)O)([CH3:18])=[CH2:17].C(=O)([O-])[O-].[K+].[K+]>C(COC)OC.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:16]([C:2]1[CH:3]=[C:4]([CH:7]=[C:8]([N+:12]([O-:14])=[O:13])[C:9]=1[O:10][CH3:11])[C:5]#[N:6])([CH3:18])=[CH2:17]

Participants

7

Reactant 4

HCID 962WaterHCID 11430Potassium CarbonateHCID 10855372(Prop-1-en-2-yl)boronic acidHCID 671405393-Bromo-4-methoxy-5-nitrobenzonitrile

Product 1

HCID 671408193-Isopropenyl-4-methoxy-5-nitrobenzonitrile

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 80711,2-DimethoxyethaneSolvent

Procedure

To a mixture of 3-bromo-4-methoxy-5-nitrobenzonitrile (6.26 g, 24.35 mmol) in dimethoxyethane (61 ml) was added water (16 ml), isopropenyl boronic acid (6.28 g, 73.1 mmol), potassium carbonate (10.10 g, 73.1 mmol), and tetrakis(triphenylphosphine) palladium(0) (0.281 g, 0.244 mmol). The resulting mixture was heated to reflux and stirred at this temperature overnight under nitrogen. The reaction mixture was then concentrated, diluted with water, and extracted with ethyl acetate (3×). The combined organics were washed with brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified by flash column chromatography using a Horizon Biotage, 65i Si column, eluting with 1 column volume of hexanes, followed by a linear gradient of ethyl acetate in hexanes from 0% to 100% over 10 column volumes to afford the title compound as a red oil.

Workup

  1. temperatureThe resulting mixture was heated
  2. temperatureto reflux
  3. concentrationThe reaction mixture was then concentrated
  4. additiondiluted with water
  5. extractionextracted with ethyl acetate (3×)
  6. washThe combined organics were washed with brine
  7. dry with materialdried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customThe residue was purified by flash column chromatography
  11. washeluting with 1 column volume of hexanes

Sources & evidence

ORD record
ord-298e1737d08e48bcb4df993827613cc8
Source dataset
uspto-grants-2013_05
Patent number
US08445480B2

Reaction notes

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