Dimethylformamide → Methyl 2-chloro-4-cyanobenzoate

HRID 1524873Notes

Reaction equation

HRID 1524873 reaction equation
Br[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([Cl:12])[CH:3]=1.[CH3:13][N:14](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:12][C:4]1[CH:3]=[C:2]([C:13]#[N:14])[CH:11]=[CH:10][C:5]=1[C:6]([O:8][CH3:9])=[O:7]

Participants

5

Reactant 2

HCID 6228DimethylformamideHCID 22058730Methyl 4-Bromo-2-chlorobenzoate

Product 1

HCID 53845357Methyl 2-chloro-4-cyanobenzoate

Reagents, catalysts & solvents 2

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

Conditions

Temperature
90 °C

Procedure

The product from Example 143 Part A (1.0 g, 4.0 mmol), Zn(CN)2 (0.52 g, 4.8 mmol), Pd(PPh3)4 (0.23 g, 0.2 mmol) were added together with 9 mL of DMF. The mixture was degassed and then heated at 90° C. for 6 h. Water and EtOAc were added to the reaction mixture. It was filtered to remove inorganic solids. The layers were separated and the EtOAc layer was washed with water and brine. It was dried over MgSO4, concentrated, and purified by flash chromatography (silica, EtOAc/hexane) to give 0.28 g of the desired product. MS: 196.1 (M+1)+.

Workup

  1. customThe mixture was degassed
  2. additionWater and EtOAc were added to the reaction mixture
  3. filtrationIt was filtered
  4. customto remove inorganic solids
  5. customThe layers were separated
  6. washthe EtOAc layer was washed with water and brine
  7. dry with materialIt was dried over MgSO4
  8. concentrationconcentrated
  9. custompurified by flash chromatography (silica, EtOAc/hexane)

Sources & evidence

ORD record
ord-dc1d1e6f02884cb5b7bfe32e9eb98163
Source dataset
uspto-grants-2015_07
Patent number
US09079860B2

Reaction notes

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