Ethyl chloroformate → 2-Methoxy-4-methyl-6-(3-nitrophenyl)-1,5(6H)-pyrimidinedicarboxylic acid, diethyl ester

HRID 1789578Notes

Reaction equation

HRID 1789578 reaction equation
[CH3:1][O:2][C:3]1[NH:4][C:5]([CH3:23])=[C:6]([C:18]([O:20][CH2:21][CH3:22])=[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.Cl[C:25]([O:27][CH2:28][CH3:29])=[O:26]>ClCCl.N1C=CC=CC=1>[CH3:1][O:2][C:3]1[N:8]([C:25]([O:27][CH2:28][CH3:29])=[O:26])[CH:7]([C:9]2[CH:14]=[CH:13][CH:12]=[C:11]([N+:15]([O-:17])=[O:16])[CH:10]=2)[C:6]([C:18]([O:20][CH2:21][CH3:22])=[O:19])=[C:5]([CH3:23])[N:4]=1

Participants

5

Reactant 2

HCID 10928Ethyl chloroformateHCID 139125831,4-Dihydro-2-methoxy-6-methyl-4-(3-nitrophenyl)-5-pyrimidinecarboxylic acid, ethyl ester

Product 1

HCID 139572682-Methoxy-4-methyl-6-(3-nitrophenyl)-1,5(6H)-pyrimidinedicarboxylic acid, diethyl ester

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of 1,4-dihydro-2-methoxy-6-methyl-4-(3-nitrophenyl)-5-pyrimidinecarboxylic acid, ethyl ester (3.19 g, 10.0 mmoles) in dry dichloromethane (15 ml) and pyridine (4 ml) was cooled to 0° C. and treated dropwise with ethyl chloroformate (1.2 ml, 12.0 mmoles) under argon. After the addition was completed, the cooling bath was removed and the reaction was allowed to stir at room temperature for 1 hour. It was then diluted with ethyl acetate and the resulting solution was washed with water, sodium bicarbonate and brine. After drying over anhydrous magnesium sulfate, the solvent was evaporated. The residue was coevaporated with toluene to remove residual pyridine. The colorless solid obtained was subjected to high vacuum and used in the next reaction without further purification (3.81 g). For analytical purposes, a small amount of the compound was recrystallized from ether-hexanes to provide colorless solid, melting point 61.5°-64.5° C.

Workup

  1. additionAfter the addition
  2. customthe cooling bath was removed
  3. additionIt was then diluted with ethyl acetate
  4. washthe resulting solution was washed with water, sodium bicarbonate and brine
  5. dry with materialAfter drying over anhydrous magnesium sulfate
  6. customthe solvent was evaporated
  7. customto remove residual pyridine
  8. customThe colorless solid obtained
  9. customused in the next reaction without further purification (3.81 g)
  10. customFor analytical purposes, a small amount of the compound was recrystallized from ether-hexanes
  11. customto provide colorless solid, melting point 61.5°-64.5° C.

Sources & evidence

ORD record
ord-13857672a37f4505a6ebafc5780a12ef
Source dataset
uspto-grants-1987_08
Patent number
US04689414

Reaction notes

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