5-Bromo-2,4-bis(1,1-dimethylethoxy)pyrimidine → 5-(2,8-Dimethyl-5h-dibenzo[a,d]cyclohepten-5-yl)-2,4(1h,3h)-pyrimidinedione

HRID 1275887Notes

Reaction equation

HRID 1275887 reaction equation
C([Li])CCC.Br[C:7]1[C:8]([O:18]C(C)(C)C)=[N:9][C:10]([O:13]C(C)(C)C)=[N:11][CH:12]=1.[CH3:23][C:24]1[CH:40]=[CH:39][C:27]2[C:28](=O)[C:29]3[CH:36]=[CH:35][C:34]([CH3:37])=[CH:33][C:30]=3[CH2:31][CH2:32][C:26]=2[CH:25]=1>O1CCCC1>[CH3:37][C:34]1[CH:35]=[CH:36][C:29]2[CH:28]([C:7]3[C:8](=[O:18])[NH:9][C:10](=[O:13])[NH:11][CH:12]=3)[C:27]3[CH:39]=[CH:40][C:24]([CH3:23])=[CH:25][C:26]=3[CH:32]=[CH:31][C:30]=2[CH:33]=1

Participants

5

Reactant 3

HCID 8188515-Bromo-2,4-bis(1,1-dimethylethoxy)pyrimidineHCID 2211720110,11-dihydro-2,8-dimethyl-5H-dibenzo[a,d]cyclohepten-5-oneHCID 178418339Butyllithium

Product 1

HCID 221172135-(2,8-Dimethyl-5h-dibenzo[a,d]cyclohepten-5-yl)-2,4(1h,3h)-pyrimidinedione

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
120 °C

Procedure

n-Butyllithium (5.6 ml of a 2.5M solution in hexanes) was added dropwise to a solution of 5-bromo-2,4-bis(1,1,-dimethylethoxy)pyrimidine (example 1 step (i)) (3.85 g) in tetrahydrofuran (30 ml) at -78° C. The solution was stirred for 30 minutes and a solution of 10,11-dihydro-2,8-dimethyl-5H-dibenzo[a,d]cyclohepten-5-one (European Patent, 1993, 0 589 322 A1) (3.0 g) in tetrahydrofuran (20 ml) was added. The mixture was stirred at -78° C. for 45 minutes and room temperature for 15 minutes and then partitioned between brine and ethyl acetate. The organic phase was dried (MgSO4) and evaporated. The residue was dissolved in glacial acetic acid (100 ml) and heated at 120° C. for 30 minutes. The solvent was evaporated and the residue azeotroped with toluene and triturated with diethyl ether to give a solid. Yield 4.03 g.

Workup

  1. stirringThe mixture was stirred at -78° C. for 45 minutes and room temperature for 15 minutes
  2. custompartitioned between brine and ethyl acetate
  3. dry with materialThe organic phase was dried (MgSO4)
  4. customevaporated
  5. dissolutionThe residue was dissolved in glacial acetic acid (100 ml)
  6. customThe solvent was evaporated
  7. customthe residue azeotroped with toluene
  8. customtriturated with diethyl ether
  9. customto give a solid

Sources & evidence

ORD record
ord-699c2f7b1b914936891c47c008b2fc04
Source dataset
uspto-grants-2000_12
Patent number
US06162808

Reaction notes

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