Hydrochloric Acid → HCID 9867103, compound

HRID 1275076Notes

Reaction equation

HRID 1275076 reaction equation
C([O:4][C:5]1[C:10]([CH3:11])=[C:9]([CH3:12])[C:8]([NH:13][CH3:14])=[C:7]([NH2:15])[C:6]=1[CH3:16])(=O)C.CO[C:19]([CH2:21][O:22][C:23]1[CH:36]=[CH:35][C:26]([CH2:27][CH:28]2[S:32][C:31](=[O:33])[NH:30][C:29]2=[O:34])=[CH:25][CH:24]=1)=O.Cl.C(=O)([O-])O.[Na+]>C(OCC)C.O1CCOCC1>[OH:4][C:5]1[C:10]([CH3:11])=[C:9]([CH3:12])[C:8]2[N:13]([CH3:14])[C:19]([CH2:21][O:22][C:23]3[CH:24]=[CH:25][C:26]([CH2:27][CH:28]4[S:32][C:31](=[O:33])[NH:30][C:29]4=[O:34])=[CH:35][CH:36]=3)=[N:15][C:7]=2[C:6]=1[CH3:16]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 516892Sodium BicarbonateHCID 22119054HCID 22119054, compoundHCID 235141985-(4-Methoxycarbonylmethyloxybenzyl)thiazolidine-2,4-dione

Product 1

HCID 9867103HCID 9867103, compoundYield 27.2%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 312751,4-DioxaneSolvent

Procedure

A mixture of 1.0 g of 4-acetoxy-N-methyl-3,5,6-trimethyl-1,2-phenylenediamine [prepared as described in step (j) above], 2.7 g of 5-(4-methoxycarbonylmethoxybenzyl)thiazolidine-2,4-dione [prepared as described in step 2(g) of Preparation 2], 5 ml of 1,4-dioxane and 25 ml of concentrated aqueous hydrochloric acid was heated under reflux for 2 days. At the end of this time, the reaction mixture was added to ice-water and the resulting mixture was neutralized by the addition of sodium hydrogencarbonate. It was then extracted with ethyl acetate. The extract was washed with a saturated aqueous solution of sodium chloride and dried over anhydrous magnesium sulfate. The solvent was then removed by distillation under reduced pressure, after which the residue was purified by column chromatography through silica gel, using ethyl acetate as the eluent. Fractions containing the title compound were collected and the solvent was removed by distillation under reduced pressure, to give a red residual oil. 150 ml of diethyl ether were added to the oil, and the mixture was agitated ultrasonically for 5 minutes. The precipitate which separated out was collected by filtration and dissolved in 300 ml of tetrahydrofuran. The resulting solution was concentrated to a volume of between about 10 ml and 20 ml by evaporation under reduced pressure. 200 ml of ethyl acetate were added to the concentrate, and the mixture was agitated ultrasonically for 20 minutes. The precipitate which separated out was collected by filtration, to give 0.52 g of the title compound, melting at 240-244° C. and having an Rf value=0.44 (on thin layer chromatography on silica gel; developing solvent: ethyl acetate).

Workup

  1. temperaturewas heated
  2. temperatureunder reflux for 2 days
  3. extractionIt was then extracted with ethyl acetate
  4. washThe extract was washed with a saturated aqueous solution of sodium chloride
  5. dry with materialdried over anhydrous magnesium sulfate
  6. customThe solvent was then removed by distillation under reduced pressure
  7. customafter which the residue was purified by column chromatography through silica gel
  8. additionFractions containing the title compound
  9. customwere collected
  10. customthe solvent was removed by distillation under reduced pressure
  11. customto give a red residual oil
  12. customThe precipitate which separated out
  13. filtrationwas collected by filtration
  14. dissolutiondissolved in 300 ml of tetrahydrofuran
  15. concentrationThe resulting solution was concentrated to a volume of between about 10 ml and 20 ml by evaporation under reduced pressure
  16. addition200 ml of ethyl acetate were added to the concentrate
  17. stirringthe mixture was agitated ultrasonically for 20 minutes
  18. customThe precipitate which separated out
  19. filtrationwas collected by filtration

Sources & evidence

ORD record
ord-a914097242af4985877fdf9c34653706
Source dataset
uspto-grants-2000_12
Patent number
US06159997

Reaction notes

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