Dichloromethane → 2-chloro-N,N-diethyl-4-methylbenzamide

HRID 2100599Notes

Reaction equation

HRID 2100599 reaction equation
Br[C:2]1[CH:14]=[CH:13][C:5]([C:6]([N:8]([CH2:11][CH3:12])[CH2:9][CH3:10])=[O:7])=[C:4]([Cl:15])[CH:3]=1.[C:16](=O)([O-])[O-].[K+].[K+].C[Zn]C.ClCCl>CN(C=O)C.C1(C)C=CC=CC=1.C(OCC)(=O)C.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[Cl:15][C:4]1[CH:3]=[C:2]([CH3:16])[CH:14]=[CH:13][C:5]=1[C:6]([N:8]([CH2:11][CH3:12])[CH2:9][CH3:10])=[O:7]

Participants

9

Reactant 4

HCID 6344DichloromethaneHCID 11430Potassium CarbonateHCID 161159314-Bromo-2-chloro-N,N-diethylbenzamideHCID 178477796HCID 178477796, compound

Product 1

HCID 8858472-chloro-N,N-diethyl-4-methylbenzamideYield 90%

Reagents, catalysts & solvents 4

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 1140TolueneSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
90 °C

Procedure

To a solution of 4-bromo-2-chloro-N,N-diethylbenzamide from Example 23, Part A (3.10 g, 10.67 mmol) in 50 mL of DMF was added potassium carbonate (3.68 g, 26.7 mmol) and dimethyl zinc (8.0 mL of a 2.0 M solution in toluene, 16.0 mmol). The solution was degassed with a stream of argon and then there was added [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium (II) complex with dichloromethane (1:1) (175 mg, 0.21 mmol). The reaction mixture was allowed to stir at 90° C. for 18 h. The reaction mixture was allowed to cool and was diluted with ethyl acetate. The organics were washed with water and brine, dried (MgSO4) and concentrated. The residue was purified (ISCO, elution with 0-50% EtOAc/hexane, 30 min) to afford 2.15 g (90%) of the title compound as a colorless oil. LRMS (ESI): 226.2/228.2 (M+H)+.

Workup

  1. customThe solution was degassed with a stream of argon
  2. temperatureto cool
  3. washThe organics were washed with water and brine
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated
  6. customThe residue was purified
  7. wash(ISCO, elution with 0-50% EtOAc/hexane, 30 min)

Sources & evidence

ORD record
ord-d7f44d05a3ba4aabbc7bcc6dd27c6bd4
Source dataset
uspto-grants-2009_08
Patent number
US07572805B2

Reaction notes

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