Benzoyl Peroxide → 1-Benzyl-2-(1-t-butoxycarbonylamino-2-methyl-propyl)-4-methyl-6-oxo-1,6-dihydro-pyrimidine-5-carboxylic Acid Methyl Ester

HRID 1455149Notes

Reaction equation

HRID 1455149 reaction equation
[CH3:1][O:2][C:3]([CH:5]1[C:10](=[O:11])[N:9]([CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[C:8]([CH:19]([NH:23][C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])[CH:20]([CH3:22])[CH3:21])=[N:7][CH:6]1[CH3:31])=[O:4].C([O-])([O-])=O.[K+].[K+].C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1.CCOC(C)=O>C(Cl)(Cl)(Cl)Cl.CCCCCC>[CH3:1][O:2][C:3]([C:5]1[C:10](=[O:11])[N:9]([CH2:12][C:13]2[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=2)[C:8]([CH:19]([NH:23][C:24]([O:26][C:27]([CH3:28])([CH3:30])[CH3:29])=[O:25])[CH:20]([CH3:22])[CH3:21])=[N:7][C:6]=1[CH3:31])=[O:4]

Participants

7

Reactant 4

HCID 7187Benzoyl PeroxideHCID 8857Ethyl AcetateHCID 11430Potassium CarbonateHCID 575311891-Benzyl-2-(1-t-butoxycarbonylamino-2-methyl-propyl)-4-methyl-6-oxo-1,4,5,6-tetrahydro-pyrimidine-5-carboxylic acid methyl ester

Product 1

HCID 575311921-Benzyl-2-(1-t-butoxycarbonylamino-2-methyl-propyl)-4-methyl-6-oxo-1,6-dihydro-pyrimidine-5-carboxylic Acid Methyl EsterYield 40.3%

Reagents, catalysts & solvents 2

HCID 5943Carbon TetrachlorideSolventHCID 8058HexaneSolvent

Procedure

To a stirred solution of 1-Benzyl-2-(1-t-butoxycarbonylamino-2-methyl-propyl)-4-methyl-6-oxo-1,4,5,6-tetrahydro-pyrimidine-5-carboxylic acid methyl ester (6.37 g, 14.8 mMol) in CCl4 (150 mL) was added K2CO3 (4.0 g, 29 mMol), N-Bromosuccinimde (2.63 g, 14.8 mMol) and Benzoyl peroxide (0.18 g, 0.74 mMol). The reaction was refluxed for 0.5 h, cooled to RT, filtered through a pad of Celite®, and rinsed with CH2Cl2. The filtrate was concentrated under vacuum and purified by flash chromatography (step gradient of 0 to 5% EtOAc in CH2Cl2). The semi-purified product obtained was taken up in a solution of 20% EtOAc in hexane (10 mL) at which point the product began to crystallize out. The mixture was diluted with a solution of 10% Et2O in pet. Et2O (50 mL), triturated, filtered and dried under vacuum to give the title compound (2.56 g, 40%) as a white solid: MS (ES) m/e 432.2 and 430.2 (M+H)+.

Workup

  1. temperatureThe reaction was refluxed for 0.5 h
  2. filtrationfiltered through a pad of Celite®
  3. washrinsed with CH2Cl2
  4. concentrationThe filtrate was concentrated under vacuum
  5. custompurified by flash chromatography (step gradient of 0 to 5% EtOAc in CH2Cl2)
  6. customThe semi-purified product obtained
  7. customto crystallize out
  8. additionThe mixture was diluted with a solution of 10% Et2O in pet
  9. customEt2O (50 mL), triturated
  10. filtrationfiltered
  11. customdried under vacuum

Sources & evidence

ORD record
ord-6e2de79b8adf45c09ef76e04499cc192
Source dataset
uspto-grants-2009_01
Patent number
US07482343B2

Reaction notes

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