Acetic Acid → 6,7-Dihydro-6-p-methoxybenzylthio-5H-pyrrolo(1,2-a)-imidazole

HRID 1088533Notes

Reaction equation

HRID 1088533 reaction equation
C(O[C:4]1[CH2:8][CH:7]([S:9][CH2:10][C:11]2[CH:16]=[CH:15][C:14]([O:17][CH3:18])=[CH:13][CH:12]=2)[CH2:6][N:5]=1)C.CO[CH:21](OC)[CH2:22][NH2:23].C(O)(=O)C.[OH-].[Na+]>CO.O.C(OCC)(=O)C>[CH3:18][O:17][C:14]1[CH:13]=[CH:12][C:11]([CH2:10][S:9][CH:7]2[CH2:6][N:5]3[CH:21]=[CH:22][N:23]=[C:4]3[CH2:8]2)=[CH:16][CH:15]=1

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 14798Sodium HydroxideHCID 89728Aminoacetaldehyde dimethyl acetalHCID 104680652-Ethoxy-4-p-methoxybenzylthio-1-pyroline

Product 1

HCID 100839776,7-Dihydro-6-p-methoxybenzylthio-5H-pyrrolo(1,2-a)-imidazole

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

2-Ethoxy-4-p-methoxybenzylthio-1-pyroline (930 mg) and aminoacetaldehyde dimethylacetal (552 mg) were dissolved in 50 ml of methanol and refluxed under heating for one hour after the addition of acetic acid (315 mg). Ethyl acetate and water were added thereto after cooling and the solution was made alkaline with lN sodium hydroxide aq. solution before subjecting to distribution therebetween. The ethyl acetate phase was washed with water and saturated aqueous solution of NaCl, then the phase was dried over Na2SO4 and concentrated in vacuo. The residue was dissolved in 70 ml of benzene, p-toluenesulfonic acid monohydrate (1 g) was added and refluxed under heating for three hours. The solvent was distilled off in vacuo, then water and ethyl acetate were added to the residue and the solvent was made alkaline with 5% aqueous solution of sodium bicarbonate before carrying out the distribution. After the ethyl acetate phase was washed with water and dried over Na2SO4, the phase was concentrated in vacuo. The residue was purified by column chromatography using a column packed with 25 g of silica gel [eluent: chloroform/methanol (19:1 v/v)] and the fractions containing the objective compound were combined and concentrated in vacuo so that the objective compound, as brown oil, was obtained (yield: 731 mg).

Workup

  1. temperaturerefluxed
  2. temperatureunder heating for one hour
  3. temperatureafter cooling
  4. washThe ethyl acetate phase was washed with water and saturated aqueous solution of NaCl
  5. dry with materialthe phase was dried over Na2SO4
  6. concentrationconcentrated in vacuo
  7. dissolutionThe residue was dissolved in 70 ml of benzene
  8. additionp-toluenesulfonic acid monohydrate (1 g) was added
  9. temperaturerefluxed
  10. temperatureunder heating for three hours
  11. distillationThe solvent was distilled off in vacuo
  12. additionwater and ethyl acetate were added to the residue
  13. washAfter the ethyl acetate phase was washed with water
  14. dry with materialdried over Na2SO4
  15. concentrationthe phase was concentrated in vacuo
  16. customThe residue was purified by column chromatography
  17. additionthe fractions containing the objective compound
  18. concentrationconcentrated in vacuo so that the objective compound, as brown oil
  19. customwas obtained (yield: 731 mg)

Sources & evidence

ORD record
ord-b3f8de679c4040109b7cd9940e78a0d2
Source dataset
uspto-grants-1990_10
Patent number
US04962202

Reaction notes

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