Dimethylformamide → HCID 57809247, compound

HRID 2105851Notes

Reaction equation

HRID 2105851 reaction equation
Br[C:2]1[C:12]([O:13][CH2:14][CH3:15])=[CH:11][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[C:4]([O:16][CH2:17][CH3:18])[CH:3]=1.[CH3:19][N:20](C)C=O>[C-]#N.[Zn+2].[C-]#N.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.O>[C:19]([C:2]1[C:12]([O:13][CH2:14][CH3:15])=[CH:11][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[C:4]([O:16][CH2:17][CH3:18])[CH:3]=1)#[N:20]

Participants

6

Reactant 2

HCID 6228DimethylformamideHCID 68870510HCID 68870510, compound

Product 1

HCID 57809247HCID 57809247, compoundYield 81%

Reagents, catalysts & solvents 3

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent

Conditions

Temperature
80 °C

Procedure

Ethyl 4-bromo-2,5-diethoxybenzoate (0.615 g, 1.94 mmol), zinc cyanide (0.137 g, 1.17 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.157 g, 0.136 mmol) were combined under nitrogen in a flame-dried Schlenk tube. Dimethylformamide (7 mL) was added and the reaction mixture was put through three freeze-pump-thaw cycles and then put under a nitrogen atmosphere and heated at 80° C. for 16 h. After cooling to room temperature, water (50 mL) was added and the resulting mixture was extracted with diethyl ether (100 mL, 2×50 mL). The combined organic phases were washed with brine (3×50 mL) and then dried over magnesium sulfate and concentrated. Purification of the crude residue by flash column chromatography (silica gel, eluting with 33% ethyl acetate in hexanes) gave ethyl 4-cyano-2,5-diethoxy-benzoate as an off-white solid (0.416 g, 81%).

Workup

  1. temperatureAfter cooling to room temperature
  2. extractionthe resulting mixture was extracted with diethyl ether (100 mL, 2×50 mL)
  3. washThe combined organic phases were washed with brine (3×50 mL)
  4. dry with materialdried over magnesium sulfate
  5. concentrationconcentrated
  6. customPurification of the crude residue
  7. washby flash column chromatography (silica gel, eluting with 33% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-9f85afe6b6464958bb205fd6bc1cf5a4
Source dataset
uspto-grants-2009_08
Patent number
US07579368B2

Reaction notes

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