Ethyl 2-(4-bromophenyl)acetate → Ethyl 2-(4-cyanophenyl)acetate

HRID 526443Notes

Reaction equation

HRID 526443 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10])=[CH:4][CH:3]=1.[C:14]([Cu])#[N:15]>[Cu]I.CN1C(=O)CCC1>[C:14]([C:2]1[CH:7]=[CH:6][C:5]([CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10])=[CH:4][CH:3]=1)#[N:15]

Participants

5

Reactant 2

HCID 7020609Ethyl 2-(4-bromophenyl)acetateHCID 178418546HCID 178418546, compound

Product 1

HCID 279718Ethyl 2-(4-cyanophenyl)acetateYield 133.2%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 13387N-methyl-2-pyrrolidoneSolvent

Conditions

Temperature
160 °C

Procedure

Combined ethyl 2-(4-bromophenyl)acetate (30 g, 0.123 mol) and NMP (200 mL). Then CuCN (33 g, 0.370 mol) was added in portions and then degassed and refilled with nitrogen three times. Then CuI (4.7 g, 0.0247 mol) was added in one portion. The reaction was degassed and refilled with nitrogen three times and then heated to 160° C. for 4 hours. Then the reaction was heated to 180° C. for another 3 hours. The solution was then cooled to room temperature and diluted with EtOAc (500 mL) and water (500 mL). After stirring for 10 mins, the reaction was filtered and the aqueous layer was extracted with EtOAc (500 mL×2). The combined organic layers were washed with brine, dried over Na2SO4 and concentrated to dryness to give the title compound (31 g, 66.5%) as a brown solid.

Workup

  1. customdegassed
  2. additionrefilled with nitrogen three times
  3. customThe reaction was degassed
  4. additionrefilled with nitrogen three times
  5. temperatureThen the reaction was heated to 180° C. for another 3 hours
  6. temperatureThe solution was then cooled to room temperature
  7. additiondiluted with EtOAc (500 mL) and water (500 mL)
  8. filtrationthe reaction was filtered
  9. extractionthe aqueous layer was extracted with EtOAc (500 mL×2)
  10. washThe combined organic layers were washed with brine
  11. dry with materialdried over Na2SO4
  12. concentrationconcentrated to dryness

Sources & evidence

ORD record
ord-c1ef4078e62d4e41bd7182644618c6c6
Source dataset
uspto-grants-2016_05
Patent number
US09345713B2

Reaction notes

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