Acetonitrile → 2-Chloro-6-(4-pyridyl)benzaldehyde

HRID 1241919Notes

Reaction equation

HRID 1241919 reaction equation
[Cl:1][C:2]1[CH:9]=[CH:8][CH:7]=[C:6](Br)[C:3]=1[CH:4]=[O:5].[N:11]1[CH:16]=[CH:15][C:14](B(O)O)=[CH:13][CH:12]=1.C(#N)C.C(=O)([O-])[O-].[Na+].[Na+]>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.CO>[Cl:1][C:2]1[CH:9]=[CH:8][CH:7]=[C:6]([C:14]2[CH:15]=[CH:16][N:11]=[CH:12][CH:13]=2)[C:3]=1[CH:4]=[O:5]

Participants

7

Reactant 4

HCID 6342AcetonitrileHCID 10340Sodium CarbonateHCID 2734379(Pyridin-4-yl)boronic acidHCID 135240422-Bromo-6-chlorobenzaldehyde

Product 1

HCID 219376462-Chloro-6-(4-pyridyl)benzaldehydeYield 51%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 887MethanolSolvent

Procedure

2-Chloro-6-bromobenzaldehyde (200 mg, 0.91 mmol), pyridine-4-boronic acid (125 mg, 1.0 mmol), dichlorobis(triphenylphosphine)palladium (II) (5 mol %, 30 mg), acetonitrile (2 mL) and aqueous sodium carbonate (2 molar solution, 2 mL) were combined in a microwave vial and sealed with a crimp seal. The mixture was microwaved at 150° C. for 5 min. The crude reaction mixture was then poured over Celite and washed with acetonitrile. The mixture was concentrated under reduced pressure and taken up in ethyl acetate. This organic solution was successively washed with water and brine, then dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The resulting residue was purified by flash column chromatography on silica gel, eluting with 98:2 methylene chloride:methanol to provide 2-chloro-6-(4-pyridyl)benzaldehyde (100 mg, 51% yield). NMR (300 MHz, CDCl3): 10.3 (s, 1H), 8.65 (m, 2H), 7.55 (m, 2H), 7.2 ppm (m, 3H).

Workup

  1. customsealed with a crimp
  2. customseal
  3. customThe mixture was microwaved at 150° C. for 5 min
  4. customThe crude reaction mixture
  5. additionwas then poured over Celite
  6. washwashed with acetonitrile
  7. concentrationThe mixture was concentrated under reduced pressure
  8. washThis organic solution was successively washed with water and brine
  9. dry with materialdried over anhydrous sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated under reduced pressure
  12. customThe resulting residue was purified by flash column chromatography on silica gel
  13. washeluting with 98:2 methylene chloride

Sources & evidence

ORD record
ord-8b949743e80044ac936a7b739ea8c881
Source dataset
uspto-grants-2006_10
Patent number
US07115642B2

Reaction notes

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