1-Butanol → HCID 86745839, compound

HRID 1196484Notes

Reaction equation

HRID 1196484 reaction equation
[CH3:1][O:2][C:3](=[O:15])[CH2:4][CH:5]([C:7](=O)[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)Cl.[NH2:16][NH:17][C:18]([NH2:20])=S.[C:21]([OH:26])(=[O:25])[C:22]([OH:24])=[O:23].[CH2:27](O)[CH2:28][CH2:29]C>>[C:21]([OH:26])(=[O:25])[C:22]([OH:24])=[O:23].[CH2:1]([O:2][C:3](=[O:15])[CH2:4][C:5]1[C:18]([NH2:20])=[N:17][NH:16][C:7]=1[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[CH2:27][CH2:28][CH3:29]

Participants

5

Reactant 4

HCID 2631-ButanolHCID 971Oxalic AcidHCID 2723789ThiosemicarbazideHCID 19898816Methyl β-chloro-γ-oxobenzenebutanoate

Product 1

HCID 86745839HCID 86745839, compound

Procedure

A mixture of 10.0 g (0.044 mole) of methyl-3-benzoyl-3-chloropropionate and 4.0 g (0.044 mole) of thiosemicarbazide in 50 ml of 1-butanol was refluxed under a nitrogen atmosphere for 32 hours. After cooling to room temperature, the precipitated sulfur was removed by filtration. The filtrate was evaporated under reduced pressure and the residue partitioned between methylene chloride and aqueous 7% sodium bicarbonate. The layers were separated and the organic layer was extracted with water, dried over magnesium sulfate and evaporated under reduced pressure. The residue was dissolved in toluene and chromatographed on an 85 g column of silica gel (47 mm×20 cm) packed in toluene. The column was washed with toluene, methylene chloride, 10% and 50% ethyl acetate-methylene chloride and ethyl acetate, respectively. The fractions containing relatively pure products were combined and evaporated under reduced pressure. The residual oil (4.7 g) was dissolved in isopropanol and treated with 1.5 g (0.017 mole) of anhydrous oxalic acid. The mixture was refluxed until solution was complete, filtered, and the filtrate was treated with isopropyl ether to the cloud point. The oxalate salt of the butyl ester was collected by filtration: 4.8 g (30%), mp 169°-172° C.

Workup

  1. temperaturewas refluxed under a nitrogen atmosphere for 32 hours
  2. customthe precipitated sulfur was removed by filtration
  3. customThe filtrate was evaporated under reduced pressure
  4. customthe residue partitioned between methylene chloride and aqueous 7% sodium bicarbonate
  5. customThe layers were separated
  6. extractionthe organic layer was extracted with water
  7. dry with materialdried over magnesium sulfate
  8. customevaporated under reduced pressure
  9. dissolutionThe residue was dissolved in toluene
  10. customchromatographed on an 85 g column of silica gel (47 mm×20 cm)
  11. washThe column was washed with toluene, methylene chloride, 10% and 50% ethyl acetate-methylene chloride and ethyl acetate
  12. additionThe fractions containing relatively pure products
  13. customevaporated under reduced pressure
  14. dissolutionThe residual oil (4.7 g) was dissolved in isopropanol
  15. temperatureThe mixture was refluxed until solution
  16. filtrationfiltered
  17. additionthe filtrate was treated with isopropyl ether to the cloud point
  18. filtrationThe oxalate salt of the butyl ester was collected by filtration

Sources & evidence

ORD record
ord-c11eb8e0abbb4c0ab42c8b522d972963
Source dataset
uspto-grants-1992_05
Patent number
US05114944

Reaction notes

Loading…