Methyl Ethyl Ketone → 1-Methyl-3-(6-methylergolin-8beta-ylmethyl)imidazolidin-2,4-dione

HRID 986525Notes

Reaction equation

HRID 986525 reaction equation
S(C1C=CC(C)=CC=1)(O[CH2:5][C@@H:6]1[CH2:20][C@H:19]2[C@@H:9]([CH2:10][C:11]3[C:21]4[C:14](=[CH:15][CH:16]=[CH:17][C:18]2=4)[NH:13][CH:12]=3)[N:8]([CH3:22])[CH2:7]1)(=O)=O.[CH3:30][N:31]1[CH2:35][C:34](=[O:36])[NH:33][C:32]1=[O:37].C(=O)([O-])[O-].[K+].[K+].C(C(C)=O)C>CN(C)C=O>[CH3:30][N:31]1[CH2:35][C:34](=[O:36])[N:33]([CH2:5][C@@H:6]2[CH2:20][C@H:19]3[C@@H:9]([CH2:10][C:11]4[C:21]5[C:14](=[CH:15][CH:16]=[CH:17][C:18]3=5)[NH:13][CH:12]=4)[N:8]([CH3:22])[CH2:7]2)[C:32]1=[O:37]

Participants

6

Reactant 4

HCID 6569Methyl Ethyl KetoneHCID 11430Potassium CarbonateHCID 692171-MethylhydantoinHCID 139330156-Methylergolin-8beta-ylmethyl tosylate

Product 1

HCID 104732081-Methyl-3-(6-methylergolin-8beta-ylmethyl)imidazolidin-2,4-dioneYield 69.9%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A mixture of 0.5 g of 6-methylergolin-8β-ylmethyl tosylate, 1.0 g of 1-methylimidazolidin-2,4-dione, 1.0 g of potassium carbonate, 10 ml of methyl ethyl ketone and 10 ml of dimethylformamide was refluxed for 4 hours with stirring, and the solvent was distilled off under reduced pressure. Water was added to the residue, and the mixture was extracted with dichloromethane. The organic layer was washed with water, dried over magnesium sulfate, and the solvent was distilled off. The residue (which was dissolved in dichloromethane and adsorbed on silica gel) was purified by silica gel column chromatography (eluted with ethyl acetate and then with ethyl acetate:isopropyl alcohol=1:1 by volume). The product was recrystallized from dichloromethane-hexane to obtain 0.3 g of the titled product as colorless needles having a melting point higher than 210° (with decomposition).

Workup

  1. temperaturewas refluxed for 4 hours
  2. distillationthe solvent was distilled off under reduced pressure
  3. additionWater was added to the residue
  4. extractionthe mixture was extracted with dichloromethane
  5. washThe organic layer was washed with water
  6. dry with materialdried over magnesium sulfate
  7. distillationthe solvent was distilled off
  8. dissolutionThe residue (which was dissolved in dichloromethane and adsorbed on silica gel)
  9. customwas purified by silica gel column chromatography (
  10. washeluted with ethyl acetate
  11. customThe product was recrystallized from dichloromethane-hexane

Sources & evidence

ORD record
ord-33a4f491c95545efbf789851762103a7
Source dataset
uspto-grants-1987_12
Patent number
US04713457

Reaction notes

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