Methyl bromoacetate → 1-Benzyl-3-methoxycarbonyl-methyl-5-nitro-2,4(1H,3H)pyrimidinedione

HRID 1744238Notes

Reaction equation

HRID 1744238 reaction equation
[CH2:1]([N:8]1[CH:13]=[C:12]([N+:14]([O-:16])=[O:15])[C:11](=[O:17])[NH:10][C:9]1=[O:18])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:19]([O:22][C:23]([O-])=O)([O-])=[O:20].[K+].[K+].Br[CH2:29]C(OC)=O>CS(C)=O.O>[CH2:1]([N:8]1[C:13]([CH3:29])=[C:12]([N+:14]([O-:16])=[O:15])[C:11](=[O:17])[N:10]([C:19]([O:22][CH3:23])=[O:20])[C:9]1=[O:18])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 3

HCID 60984Methyl bromoacetateHCID 129887581-Benzyl-5-nitropyrimidine-2,4(1H,3H)-dioneHCID 86587255Potassium dicarbonate

Product 1

HCID 865872541-Benzyl-3-methoxycarbonyl-methyl-5-nitro-2,4(1H,3H)pyrimidinedioneYield 81%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolvent2×HCID 962WaterSolvent

Conditions

Temperature
40 °C

Procedure

EX-1A) A solution of 1-benzyl-5-nitro-2,4(1H,3H) pyrimidinedione (6.14 g, 24.82 mmol) prepared as described by Vampa, G. and Pecorari P. Boll. Chim. Farm. 1987,126, 467–469 was dissolved in 100 mL dimethylsulfoxide and potassium dicarbonate (3.78 g, 27.34 mmol) was added in one portion with stirring. After approximately 10 minutes a solution of methyl bromoacetate (2.50 mL, 26.40 mmol) in 20 mL dimethylsulfoxide was added drop wise over a 10 minute period. The reaction mixture was then heated to 40° C. and allowed to stir for 18 hours. The reaction mixture was diluted with water (500 mL). The aqueous solution was extracted with ethyl acetate (4×100 mL). The combined organic solutions were washed with water (1×150 mL), brine (2×150 mL). The organic solution was dried (MgSO4), filtered, and concentrated to give an oil. The crude oil was purified by MPLC (20% ethyl acetate/hexanes) to give pure 1-Benzyl-3-methoxycarbonyl-methyl-5-nitro-2,4(1H,3H)pyrimidinedione (EX-1A) as a white solid in 81% yield: 1H NMR (400 MHz, CDCl3) δ 8.73 (s, 1H) 7.38–7.30 (m, 5H), 5.06 (s, 2H), 4.69 (s, 2H), 3.72 (s, 3H); HRMS (ES) calcd for C14H13N3O6 319.0804, found 319.0797.

Workup

  1. stirringto stir for 18 hours
  2. extractionThe aqueous solution was extracted with ethyl acetate (4×100 mL)
  3. washThe combined organic solutions were washed with water (1×150 mL), brine (2×150 mL)
  4. dry with materialThe organic solution was dried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customto give an oil
  8. customThe crude oil was purified by MPLC (20% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-e44a0e2475c84519a6778609b7d1a570
Source dataset
uspto-grants-2006_03
Patent number
US07015230B1

Reaction notes

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