Methyl 3-aminocrotonate → HCID 57111083, compound

HRID 615136Notes

Reaction equation

HRID 615136 reaction equation
[CH3:1][S:2]([C:5](=[CH:9][C:10]1[CH:11]=[N+:12]([O-:16])[CH:13]=[CH:14][CH:15]=1)[C:6]([CH3:8])=O)(=[O:4])=[O:3].[CH3:17][O:18][C:19](=[O:24])/[CH:20]=[C:21](\[NH2:23])/[CH3:22]>C(O)C>[CH3:17][O:18][C:19]([C:20]1[CH:9]([C:10]2[CH:11]=[N+:12]([O-:16])[CH:13]=[CH:14][CH:15]=2)[C:5]([S:2]([CH3:1])(=[O:4])=[O:3])=[C:6]([CH3:8])[NH:23][C:21]=1[CH3:22])=[O:24]

Participants

4

Reactant 2

HCID 643918Methyl 3-aminocrotonateHCID 70439556HCID 70439556, compound

Product 1

HCID 57111083HCID 57111083, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A mixture of 22.5 g of 1-methylsulphonyl-1-(1-oxido-3-pyridylmethylene)-acetone, 16.5 g of 3-aminocrotonic acid methyl ester and 45 g of molecular sieve (Union Carbide, 3 Å) in 250 ml of absolute ethanol is boiled under reflux for 18 hours. The resulting suspension is filtered, the filter residue is washed with chloroform and the filtrate is concentrated by evaporation under reduced pressure. The oily residue is dried by the addition of toluene and renewed concentration by evaporation under reduced pressure. The residue is chromatographed over approximately 50 to 100 times the amount of silica gel, a mixture of chloroform and methanol (9:1) being used as the liquid phase. Once the starting materials and intermediate have been removed by washing, the desired product is eluted; the corresponding fractions are combined and concentrated by evaporation and the residue is recrystallised from a mixture of isopropanol and diethyl ether. In this manner 2,6-dimethyl-5-methylsulphonyl-4-(1-oxido-3-pyridyl)-1,4-dihydropyridine-3-carboxylic acid methyl ester having a melting point of 236°-238° is obtained.

Workup

  1. temperatureunder reflux for 18 hours
  2. filtrationThe resulting suspension is filtered
  3. washthe filter residue is washed with chloroform
  4. concentrationthe filtrate is concentrated by evaporation under reduced pressure
  5. dry with materialThe oily residue is dried by the addition of toluene
  6. concentrationconcentration
  7. customby evaporation under reduced pressure
  8. customThe residue is chromatographed over approximately 50 to 100 times the amount of silica gel
  9. additiona mixture of chloroform and methanol (9:1)
  10. customOnce the starting materials and intermediate have been removed
  11. washby washing
  12. washthe desired product is eluted
  13. concentrationconcentrated by evaporation
  14. customthe residue is recrystallised from a mixture of isopropanol and diethyl ether

Sources & evidence

ORD record
ord-00ffdb5f7c454037a1d31df94e1cb212
Source dataset
uspto-grants-1985_02
Patent number
US04497808

Reaction notes

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