Pyridine → HCID 19769619, compound

HRID 1722407Notes

Reaction equation

HRID 1722407 reaction equation
C[O:2][C:3]1[NH:4][C:5]([CH3:33])=[C:6]([C:18]([O:20][C@@H](C)CN(C)CC2C=CC=CC=2)=[O:19])[CH:7]([C:9]2[CH:14]=[CH:13][CH:12]=[C:11]([N+:15]([O-:17])=[O:16])[CH:10]=2)[N:8]=1.N1C=CC=CC=1.C1C([N+]([O-])=O)=CC=C([Cl-][C:50]([O-:52])=[O:51])C=1>ClCCl>[CH3:33][C:5]1[NH:4][C:3](=[O:2])[N:8]([C:50]([OH:52])=[O:51])[CH:7]([C:9]2[CH:14]=[CH:13][CH:12]=[C:11]([N+:15]([O-:17])=[O:16])[CH:10]=2)[C:6]=1[C:18]([OH:20])=[O:19]

Participants

4

Reactant 2

HCID 1049PyridineHCID 14855119HCID 14855119, compound

Product 1

HCID 19769619HCID 19769619, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of 1,4-dihydro-2-methoxy-6-methyl-4-(3-nitrophenyl)-5-pyrimidinecarboxylic acid, (S)-1-methyl-2-[methyl(phenylmethyl)amino]ethyl ester (2.20 g, 4.87 mmol) and pyridine (2.36 ml, 29.2 mmol) in dichloromethane (20 ml) in an ice bath under argon was treated dropwise, via addition funnel, with a solution of 4-nitrophenylchloroformate (1.08 g, 5.36 mmol) in dichloromethane (20 ml). The reaction was then stirred in the ice bath for 15 minutes and evaporated. The residue was coevaporated with toluene to remove pyridine. The residue was then taken up in tetrahydrofuran (50 ml) and methanol (25 ml) and treated with 3N hydrochloric acid (5.0 ml, pH 1). After stirring at ambient temperature for 1.5 hours, the reaction was quenched by pouring into cold (ice bath) saturated sodium bicarbonate. After evaporating to near dryness, the mixture was extracted with ethyl acetate. The combined organic phase was washed with saturated sodium chloride, dried (potassium carbonate), and evaporated to give 3,4-dihydro-6-methyl-4-(3-nitrophenyl)-2-oxo-3,5-pyrimidinedicarboxylic acid, 5[(S)-1-methyl-2-[methyl(phenylmethyl)methyl)amino)ethyl], 3-(4-nitrophenyl)ester as a brown solid (2.38 g, 83%). TLC (10% acetone/dichloromethane) two major spots, Rf =0.25 and 0.39.

Workup

  1. customevaporated
  2. customto remove pyridine
  3. additionmethanol (25 ml) and treated with 3N hydrochloric acid (5.0 ml, pH 1)
  4. customthe reaction was quenched
  5. additionby pouring into cold (ice bath) saturated sodium bicarbonate
  6. customAfter evaporating
  7. extractionthe mixture was extracted with ethyl acetate
  8. washThe combined organic phase was washed with saturated sodium chloride
  9. dry with materialdried (potassium carbonate)
  10. customevaporated

Sources & evidence

ORD record
ord-d2f2215e43f04dda8bf2252bf66e4361
Source dataset
uspto-grants-1989_08
Patent number
US04855301

Reaction notes

Loading…