Sodium Carbonate → 5-(4-Bromo-3,5-dimethylphenyl)pyrimidine

HRID 237469Notes

Reaction equation

HRID 237469 reaction equation
[Br:1][C:2]1[C:7]([CH3:8])=[CH:6][C:5](I)=[CH:4][C:3]=1[CH3:10].CC1(C)C(C)(C)OB([C:19]2[CH:20]=[N:21][CH:22]=[N:23][CH:24]=2)O1.C([O-])([O-])=O.[Na+].[Na+]>CN(C)C=O>[Br:1][C:2]1[C:7]([CH3:8])=[CH:6][C:5]([C:19]2[CH:20]=[N:21][CH:22]=[N:23][CH:24]=2)=[CH:4][C:3]=1[CH3:10]

Participants

5

Reactant 3

HCID 10340Sodium CarbonateHCID 4192667Pyrimidine-5-boronic acid, pinacol esterHCID 207480372-Bromo-5-iodo-1,3-dimethylbenzene

Product 1

HCID 866971325-(4-Bromo-3,5-dimethylphenyl)pyrimidine

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
60 °C

Procedure

In a microwave vial 2-bromo-5-iodo-1,3-dimethylbenzene (1 g) and 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrimidine (665 mg) are suspended in N,N-dimethylformamide (15 mL) and Na2CO3 (4 mL of a 2 M aqueous solution). The mixture is purged for 5 minutes with argon. [1,1′-Bis(diphenylphosphino)-ferrocene]-dichloropalladium dichloromethane complex (85 mg) is added, the vial is sealed and the mixture is stirred at 60° C. for 3 hours. After cooling to room temperature the mixture is Partitioned between water and ethyl acetate. The aqueous phase is extracted with ethyl acetate and the combined organic phases are washed with brine. Then the organic phase is dried (MgSO4) and concentrated. The residue is chromatographed on silica gel (cyclohexane/ethyl acetate 80:20→50:50) to give the title compound. Yield: 446 mg; LC (method 9): tR=1.05 min; Mass spectrum (ESI+): m/z=263 [M+H]+.

Workup

  1. customThe mixture is purged for 5 minutes with argon
  2. addition[1,1′-Bis(diphenylphosphino)-ferrocene]-dichloropalladium dichloromethane complex (85 mg) is added
  3. customthe vial is sealed
  4. temperatureAfter cooling to room temperature the mixture
  5. customis Partitioned between water and ethyl acetate
  6. extractionThe aqueous phase is extracted with ethyl acetate
  7. washthe combined organic phases are washed with brine
  8. dry with materialThen the organic phase is dried (MgSO4)
  9. concentrationconcentrated
  10. customThe residue is chromatographed on silica gel (cyclohexane/ethyl acetate 80:20→50:50)

Sources & evidence

ORD record
ord-3a2e6cd4874045e79c89d12892dede3d
Source dataset
uspto-grants-2014_02
Patent number
US08642585B2

Reaction notes

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