1,1-Ethanediol → Diethyl 1,4-dihydro-2,6-diisopropyl-4-(4-fluorophenyl)pyridine-3,5-dicarboxylate

HRID 324788Notes

Reaction equation

HRID 324788 reaction equation
[CH3:1][CH:2]([C:4](/[C:6](/[C:15]([O:17][CH3:18])=[O:16])=[CH:7]\[C:8]1[CH:13]=[CH:12][C:11]([F:14])=[CH:10][CH:9]=1)=O)[CH3:3].[NH2:19][C:20]([CH:27]([CH3:29])[CH3:28])=[CH:21][C:22]([O:24][CH2:25][CH3:26])=[O:23].[CH:30](O)(O)C>>[CH:2]([C:4]1[NH:19][C:20]([CH:27]([CH3:28])[CH3:29])=[C:21]([C:22]([O:24][CH2:25][CH3:26])=[O:23])[CH:7]([C:8]2[CH:13]=[CH:12][C:11]([F:14])=[CH:10][CH:9]=2)[C:6]=1[C:15]([O:17][CH2:18][CH3:30])=[O:16])([CH3:3])[CH3:1]

Participants

4

Reactant 3

HCID 1512111,1-EthanediolHCID 14652698Methyl (2E)-2-[(4-fluorophenyl)methylidene]-4-methyl-3-oxopentanoateHCID 59557418Ethyl 3-amino-4-methyl-pent-2-enoate

Product 1

HCID 11661355Diethyl 1,4-dihydro-2,6-diisopropyl-4-(4-fluorophenyl)pyridine-3,5-dicarboxylate

Conditions

Temperature
0 °C

Procedure

528 g (2 mol) of (E/Z)-4-carboxymethyl-5-(4-fluorophenyl)-2-methyl-pent-4-en-3-one and 350 g (2 mol) of 90% ethyl 3-amino-4-methyl-pent-2-enoate are stirred in 1800 ml ethanediol overnight at a bath temperature of 200° C. The mixture is cooled slowly and poured into a large glass beaker at approx. 80° C. After further cooling to 0° C., the solution is drawn off by suction from the precipitated sediment, then the sediment is washed well with ice cold ethanol and dried in a desiccator. The ethanol solution is concentrated, and the residue together with the ethanediol mother liquor is extracted four times with 1.5 l ether each time. The combined ether phases are washed three times each with 500 ml of 10% hydrochloric acid and once each with 500 ml of saturated sodium hydrogen carbonate solution and water, dried over magnesium sulfate, filtered, and allowed to stand overnight at room temperature. The solution is drawn off by suction from the precipitated sediment, subsequently washed with ice cold ethanol, and dried in a desiccator. The ethanol solution and the ether mother liquor are concentrated together in a vacuum to a volume of approx. 2 l, allowed to stand overnight again, and drawn off by suction from the precipitated sediment.

Workup

  1. temperatureThe mixture is cooled slowly
  2. additionpoured into a large glass beaker at approx. 80° C
  3. washthe sediment is washed well with ice cold ethanol
  4. customdried in a desiccator
  5. concentrationThe ethanol solution is concentrated
  6. extractionthe residue together with the ethanediol mother liquor is extracted four times with 1.5 l ether each time
  7. washThe combined ether phases are washed three times each with 500 ml of 10% hydrochloric acid
  8. dry with materialonce each with 500 ml of saturated sodium hydrogen carbonate solution and water, dried over magnesium sulfate
  9. filtrationfiltered
  10. washsubsequently washed with ice cold ethanol
  11. customdried in a desiccator
  12. concentrationThe ethanol solution and the ether mother liquor are concentrated together in a vacuum to a volume of approx. 2 l
  13. waitto stand overnight

Sources & evidence

ORD record
ord-060d4c7aef4048e9bbd9a36f2d134701
Source dataset
uspto-grants-2001_04
Patent number
US06218431B1

Reaction notes

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