Hydrochloric Acid → Diisopropyl Ether

HRID 1590283Notes

Reaction equation

HRID 1590283 reaction equation
C[O:2][C:3]1[NH:4][C:5]([CH3:23])=[C:6]([C:17]([O:19][CH:20]([CH3:22])[CH3:21])=[O:18])[CH:7]([C:9]2[CH:14]=[CH:13][CH:12]=[C:11]([Cl:15])[C:10]=2[Cl:16])[N:8]=1.N1C=CC=C[CH:25]=1.Cl[C:31]([O:33][CH2:34][CH3:35])=[O:32].Cl>ClCCl.CO>[CH:20]([O:19][CH:17]([CH3:6])[CH3:25])([CH3:21])[CH3:22].[Cl:16][C:10]1[C:11]([Cl:15])=[CH:12][CH:13]=[CH:14][C:9]=1[CH:7]1[N:8]([C:31]([O:33][CH2:34][CH3:35])=[O:32])[C:3](=[O:2])[NH:4][C:5]([CH3:23])=[C:6]1[C:17]([O:19][CH:20]([CH3:22])[CH3:21])=[O:18]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 1049PyridineHCID 10928Ethyl chloroformateHCID 14801747HCID 14801747, compound

Product 2

HCID 7914Diisopropyl EtherHCID 86746707HCID 86746707, compound

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of 1,4-dihydro-2-methoxy-6-methyl-4-(2,3-dichlorophenyl)-5-pyrimidinecarboxylic acid, 1-methylethyl ester (1.2 g., 3.37 mmole) and pyridine (1.0 ml.) in dichloromethane (10 ml.) under argon is cooled to 0° and treated dropwise with ethyl chloroformate (0.4 ml., 4.04 mmole). After the addition is completed, the cooling bath is removed and the reaction is allowed to stir at room temperature for one hour. The solvent is then stripped off to provide a colorless solid. This crude material is dissolved in methanol (12 ml.) and treated with 2N hydrochloric acid (3 ml.). The reaction is allowed to stir at room temperature overnight precipitating a colorless solid. The solvent is evaporated and the residue is dissolved in ethyl acetate. The resulting solution is washed with water, sodium bicarbonate solution, and brine. After drying over anhydrous magnesium sulfate, the solvent is stripped off and the residue is triturated with isopopyl ether to give 1.12 g. of colorless solid. Recrystallization from dichloromethane--isopropyl ether gives 6-(2,3-dichlorophenyl)-3,6-dihydro-4-methyl-2-oxo-1,5(2H)-pyrimidinedicarboxylic acid, 1-ethyl 5-(1-methylethyl) ester as a colorless solid; m.p. 173°-175°. TLC (silica gel; ethyl acetate: hexanes, 60:40) Rf =0.30.

Workup

  1. additionAfter the addition
  2. customthe cooling bath is removed
  3. customto provide a colorless solid
  4. stirringto stir at room temperature overnight
  5. customprecipitating a colorless solid
  6. customThe solvent is evaporated
  7. dissolutionthe residue is dissolved in ethyl acetate
  8. washThe resulting solution is washed with water, sodium bicarbonate solution, and brine
  9. dry with materialAfter drying over anhydrous magnesium sulfate
  10. customthe residue is triturated with isopopyl ether
  11. customto give 1.12 g
  12. customRecrystallization from dichloromethane

Sources & evidence

ORD record
ord-61e2a52e2c904e7e93c2a0175b8dc731
Source dataset
uspto-grants-1993_04
Patent number
US05202330

Reaction notes

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