Water → 4-Chloro-2-methoxybenzonitrile

HRID 272679Notes

Reaction equation

HRID 272679 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5](I)=[C:4]([O:9][CH3:10])[CH:3]=1.O.[CH3:12][N:13](C=O)C>[C-]#N.[C-]#N.[Zn+2].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:12]#[N:13])=[C:4]([O:9][CH3:10])[CH:3]=1

Participants

6

Reactant 3

HCID 962WaterHCID 6228DimethylformamideHCID 160792304-Chloro-1-iodo-2-methoxybenzene

Product 1

HCID 242129684-Chloro-2-methoxybenzonitrileYield 90%

Reagents, catalysts & solvents 2

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 178418397HCID 178418397, compoundCatalyst

Procedure

A mixture of Example 59A (2.68 g, 10 mmol), Zn(CN)2 (0.654 g, 5.5 mmol), and Pd(PPh3)4 (0.577 g, 0.5 mmol) in DMF (15 mL) was stirred at 90° C. for 6 hours and cooled to room temperature. The reaction mixture was poured into water (500 mL) and extracted with ethyl acetate several times. The combined extracts were washed with water and brine, dried (MgSO4), filtered, and concentrated under vacuum. The residue was purified by flash column chromatography on silica gel with 9:1 hexanes/ethyl acetate to provide 1.34 g (90%) of the desired product. MS (DCI) m/e 168 (M+H)+; 1H NMR (300 MHz, CDCl3) δ 7.49 (d, J=8.1 Hz, 1H), 6.97-7.03 (m, 2H).

Workup

  1. extractionextracted with ethyl acetate several times
  2. washThe combined extracts were washed with water and brine
  3. dry with materialdried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated under vacuum
  6. customThe residue was purified by flash column chromatography on silica gel with 9:1 hexanes/ethyl acetate

Sources & evidence

ORD record
ord-a6147602c9994a7d94c3fc524aa286bf
Source dataset
uspto-grants-2008_11
Patent number
US07456169B2

Reaction notes

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